CN109219642A

CN109219642A - With the functionalized polymer of end 1,1- disubstituted olefin monomer and other compounds and methods

Info

Publication number: CN109219642A
Application number: CN201780032319.4A
Authority: CN
Inventors: A·帕苏利; J·M·萨利文; K·K·普拉布; A·多希; A·霍尔泽; M·雷尔曼
Original assignee: Cyrus Ltd By Share Ltd
Current assignee: Cyrus Ltd By Share Ltd; Sirrus Inc
Priority date: 2016-06-03
Filing date: 2017-05-24
Publication date: 2019-01-15
Also published as: JP2021091905A; JP2019517599A; EP3464483A1

Abstract

A kind of functionalized compounds, the functionalized compounds include the residue of one or more 1,1- disubstituted olefin compounds.Preferably, the functionalized compounds include the residue of two or more 1,1- disubstituted olefin compounds, are spaced apart.The functionalized compounds can be prepared by ester exchange reaction.The functionalized compounds can be used in polymerisable compound, and can be used for preparing novel polymer (such as by reacting olefin group).

Description

With the functionalized polymer of end 1,1- disubstituted olefin monomer and other compounds and Its method

Related application

The U.S. Provisional Patent Application 62/ that patent application claims Palsule et al. was submitted on November 14th, 2016 U.S. Provisional Patent Application 62/345,334 that 421,754 priority, Palsule et al. were submitted on June 3rd, 2016, U.S. Patent application No.15/592,820, Palsule that Palsule et al. was submitted on May 11st, 2017 et al. was in 2017 years U.S. Patent application No.15/437,164 and Palsule submitted for 20 days 2 months et al. is in the beauty submitted on the 11st of August in 2016 State patent application No.15/234,191 priority, the content of these patent applications, which is incorporated by reference, to be incorporated herein.

Technical field

Disclose new compound and the combination of the polymer containing useful one or more functionalized molecules with alkenyl Object.It also discloses and prepares this new compound and composition and cross-linked polymer and block including this new compound The method of copolymer.Molecule with alkenyl is preferably 1,1- diester -1- olefin(e) compound.Preferably, polymer includes more A alkenyl spaced apart.For example, polymer can have centre polymer part, and the molecule with alkenyl is connected to center and gathers One or more ends of polymer portion.Preferred centre polymer part includes one or more polyalcohols, substantially by one Kind or a variety of polyalcohols composition are made of one or more polyalcohols completely.

Background technique

Polymer such as polyester, polycarbonate and other polyalcohols are usually the molecule of linear chain or branched chain, are not had usually There are unsaturated functional group, such as alkenyl.

1,1- diester -1- alkene such as methylene malonate diglyceride group containing there are two, and alkylidene is located at two Between diglyceride group.The latest developments for synthesizing these compounds promote the synthesis and its in various applications of these compounds It uses, referring to Malofsky US 8,609,885, US 8,884,051 and US 9,108,914；These entireties are to quote Mode is incorporated herein with for all purposes.It also developed the method for carrying out transesterification to these compounds recently. WO 2013/059473, the US 2014/0329980 of Malofsky et al., which is incorporated by reference, to be incorporated herein for owning Purpose, it is disclosed that preparing multifunctional methylene malonate by a variety of synthetic schemes.Method disclosed in a kind of is included in Make methylene malonate and polyol reaction with prepare compound, in the compound, methylene third in the presence of catalyst Ester group experience transesterification on two acid esters with polyol reaction and form polyfunctional compound (polyfunctional group mean to deposit In more than one methylene propylmalonic acid core cell).Disclose the purposes of enzymatic.Sullivan was mentioned on July 31st, 2015 The United States serial 14/814961 of friendship discloses the transesterification of 1,1-, the bis- substitution -1- alkene carried out using certain acid catalysts, The document, which is incorporated by reference, to be incorporated herein with for all purposes.

Need to can be used for preparing the composition of polyester, the polyester can be in the feelings without using catalyst of problems It is crosslinked well under condition and using relatively mild condition.It needs by the painting of this composition preparation for showing enhancing characteristic Material, the enhancing characteristic include flexibility, with the adhesiveness of substrate, pencil hardness, solvent resistance, wearability, uviolresistance, Heat-resisting quantity etc..The method for needing to prepare the component for this coating and coating.

Summary of the invention

One aspect of the present invention is related to being functionalized polyol, and it includes central part (preferably isocyanuric acid esters Tripolymer or centre polymer part)；And 1, two or more residues of 1- disubstituted olefin compound, wherein two replace One or two of group includes ester group；During wherein each of the residue of the substitution of 1,1- bis- 1- olefin(e) compound is connected to The different ends of center portion point；So that functionalized polymeric has at least two olefin functionalities spaced apart.Central part is preferred Ground is formed by polyol.Central part can be isocyanurate trimer, and 1,1- disubstituted olefin compound It can be spaced apart by isocyanurate trimer.Central part may include two or more ends, and the end is by five or more Multiple atomic separations are opened, wherein each of the residue of 1,1- bis- substitution 1- olefin(e) compound is connected to the difference of central part End.

Into centre polymer part add alkenyl with formed functionalized polymeric provide for make centre polymer with The novel site of other molecules reaction.For example, alkenyl can be used for centre polymer is partially grafted on another polymer.Again Such as, multiple alkenyls spaced apart may be connected to centre polymer part to form more block structures, such as wherein centre polymer It is attached partially to the network structure of multiple blocks of second polymer part.Alkenyl can be in the polymerization process of the monomer containing alkenyl Middle copolymerization.This polymerization can be free radical polymerization, anionic polymerisation or cationic polymerization.Anionic polymerisation may include international special (Sullivan et al. submits, is published as WO on March 17th, 2016 benefit application PCT/US15/48846 on September 8th, 2015 2016/040261A1), U.S. Patent Application Publication 2016/0068616A (Palsule et al., on March 10th, 2016 announce) and One or more features described in 9,249,265 B1 of United States Patent (USP) (Stevenson et al. is issued on 2 2nd, 2016), often Piece document, which is incorporated by reference, to be incorporated to.For another example, functionalized polymeric can be used cross-linking compounds (for example, sulfur-crosslinked chemical combination Object or non-sulfur-crosslinked compound) and/or can be formed in the cross-linking aid of bridge between two or more alkenyls and be crosslinked.

Centre polymer part may include one or more polyalcohols, be substantially made of one or more polyalcohols or It is made of completely one or more polyalcohols.One or more polyalcohols can be one or more polyether polyol, gather Siloxane polyol, polycarbonate polyol, polyester polyol, polyethylene glycol, acrylic polyol or polybutadiene polyol. One or more polyalcohols can be tool, and there are two the straight chains of chain end, or can be with 3 or more last-in-chain(LIC)s The branch at end.Preferably, one or more of chain end, two or more or can all have and can be reacted with ester group Hydroxyl.Hydroxyl can also dangle on the main chain of polyalcohol.For example, functional compound may include ester group, and ester can be passed through Exchange reaction is connected to polyalcohol.The example of ester exchange reaction includes 2016/0221922 A1 of U.S. Patent Application Publication US (Sullivan et al., on August 4th, 2016 announce) and U.S. Patent application No.15/234,191 (Palsule et al., 2016 August 11 days submit) disclosed in those, these documents, which are incorporated by reference, to be incorporated herein.Polyalcohol may include one or Multiple, two or more or three or more hydroxyls.

Functionalized polymeric disclosed herein can be made into film or coating.The thickness of coating or film can be about 0.001 μm or Bigger, about 0.1 μm or bigger, about 1 μm or bigger or about 2 μm or bigger.The thickness of coating or film is preferably from about 200 μm or more It is small, more preferably about 50 μm or smaller, most preferably about 20 μm or smaller.

Functional compound with alkenyl can be 1,1- disubstituted olefin compound.1,1- disubstituted olefin compound packet It includes single described in 2016/0068616 A1 of U.S. Patent Application Publication US (for example, with reference to paragraph 0022 and 0030-0045) Body, the document are herein incorporated by reference.This functional compound can have single alkenyl, be also possible to polyfunctional (tool There are two or more alkenyl).Polyfunctional compound with multiple alkenyls includes U.S. Patent Application Publication US 2016/ Those of described in 0068616 A1 (see, for example, paragraph 0042), the document is herein incorporated by reference.Preferably, 1,1- Some or all of disubstituted olefin compound has single alkenyl.

Functionalized polymeric may be present in solvent.

(for example, substantially or entirely without solvent) can be concentrated in functionalized polymeric.In concentrate system, any solvent Amount be preferably about 10 weight % or less, about 5 weight % or less, about 2 weight % or less or about 1 weight % or more It is few.The amount of solvent can be about 0 weight % or more or about 0.1 weight % or more.

Disclose a kind of polymerisable compound comprising i) have one or more alkenyls functionalized polymeric and Ii) the one or more monomers that can polymerize with the alkenyl of functionalized polymeric.Preferably, one or more of monomers include It is one or more 1,1- diester -1- alkene, consisting essentially of or be made from it completely.

Disclose a kind of cross-linked network comprising pass through the polymer blocks for the first polymer that the second block connects, institute The second block is stated to include one or more 1,1- diester -1- alkene or be made from it completely.First polymer block is preferably For polyalcohol (for example, the polyalcohol of centre polymer part as described herein).

A kind of functionalization polyol is disclosed, it includes the polymerized polyalcohols with two or more ends Central part, wherein the residue of 1, the 1- disubstituted olefin compound of the one or more in end blocks, wherein functionalization is more Hydroxy compounds is functionalized polymeric.

Disclose it is a kind of and making 1,1- bis- that 1- olefin(e) compound be replaced to react with polyhydric alcohol polymer in successive reaction The method that functionalization polyol is formed in (for example, using tubular reactor), this method includes step of transesterification.It is preferred that Ground, tubular reactor are filled with or otherwise include one or more catalyst.

A kind of functionalization polyol is disclosed, it includes: centre polymer part, centre polymer part tool There are two or more ends being spaced apart by multiple monomeric units, the monomeric unit includes the adjacent monomer list of covalent bonding Member；Wherein centre polymer part is the homopolymer being substantially made of identical monomeric unit, or having includes first single The copolymer of the monomeric unit of body and one or more comonomers for being different from the first monomer；Wherein centre polymer part Monomeric unit includes end monomer unit at each of the end of centre polymer part place；And 1,1- disubstituted olefin One or more residues of compound, wherein one or two of disubstituted group includes ester group；Wherein 1,1- bis- replaces 1- Each of residue of olefin(e) compound is connected to the different ends of centre polymer part (that is, being connected to centre polymer Partial different end monomer units) or dangle on centre polymer part；So that functionalized polymeric has at least one Olefin functionalities.Preferably, functionalization polyol is that functionalized polymeric (preferably has 4 or more monomer lists Member).

Disclose a kind of method using monomer 1,1- diester -1- alkene crosslinking polyalcohol.

Disclose a kind of graft polymers comprising one or more 1,1- diester -1- alkene or consisting essentially of, And including one or more grafts.Graft can be polyalcohol.Preferred graft includes polyester, polyethers, polybutadiene Alkene, polycarbonate, polyethylene glycol, polymer containing acrylic acid or silicone-containing polymer.

It discloses and a kind of polyalcohol is grafted on the polymer including one or more 1,1- diester -1- olefinic monomers Method.Preferably, grafting occurs during monomer polymerization.For example, grafting can be in the copolymerization for the alkenyl being connected on polyalcohol Period occurs.

Disclose a kind of product comprising by making one or more polymerisable monomers and there is polyol backbone and one Kind, the functionalized polymer reaction of two or more ends 1,1- disubstituted olefin and the coating formed.Polymerisable monomer is excellent Choosing includes one or more 1,1- disubstituted olefins, consisting essentially of or be made from it completely.It is highly preferred that polymerizable Monomer includes one or more methylene malonates.The concentration of one or more polymerisable monomers can be about 1 weight % or more Greatly, more preferably about 10 weight % or bigger, and most preferably about 28 weight % or bigger.It is one or more polymerizable The amount of monomer can be about 98 weight % or smaller, it is therefore preferable to about 90 weight % or smaller, and most preferably about 80 weights Measure % or smaller.Coating may be affixed in any substrate.For example, substrate can be metallic substrates, polymeric substrates, fiber base Bottom, substrate of glass or ceramic bases.

Detailed description of the invention

Figure 1A is the illustrative proton NMR spectra of reaction mixture, which includes DEMM and blocked with DEMM Terate polyalcohol.

Figure 1B is the illustrative proton NMR spectra for amplifying Figure 1A of 6.5ppm methylene base region.The methylene third of transesterification The amount of diethyl adipate (monosubstituted and two substitutions) is about 29.92%, and the amount of unreacted diethyl methylenemalonate is about 70.08%.

Fig. 2 is exemplary thermal gravimetric analysis (TGA) curve with the DEMM of the aliphatic polyester polylol crosslinking of sealing end.Aliphatic series Polyester polyol can be blocked with DEMM residue.

Fig. 3 be polycarbonate polyol (above) and in excessive DEMM with DEMM block transesterification polycarbonate polyol The illustrative proton NMR stacking chart of alcohol (following figure).Disappearance/displacement of the methene proton from the 3.6ppm in polyalcohol after the reaction Show almost transesterification

Fig. 4 A is the illustrative full scale proton of sealing end (for example, with DEMM residue) polybutadiene in excessive DEMM NMR.Transesterification, which is approved really by the way that there is no the peaks at 4.1ppm, to be observed, the peak, which corresponds to, to be connected in polyalcohol The methylene of OH functional group.

Fig. 4 B is the illustrative amplifier section of the proton NMR spectra of 4A above, shows the methylene occurred at 4.1ppm The consumption of matrix.

Fig. 5 A is the illustrative full scale proton NMR of the transesterification of DEMM and polyethylene glycol PEG 300.It can be in the Asia 6.5ppm The formation of novel substance is confirmed in methyl (double bond) region.

Fig. 5 B is the illustrative proton NMR spectra of 300 polyalcohol of polyethylene glycol PEG of sealing end, shows the spectrogram in 5A The region 6.5ppm in two kinds of substances.The amount of transesterification substance is about 35%, and the amount of unreacted DEMM is about 65%.

Fig. 6 A is the illustrative proton NMR spectra of the transesterification of DEMM and glycerol ethoxylate.It can be in 6.5ppm methylene The formation of novel substance is confirmed in base (double bond) region.

Fig. 6 B is illustrative proton NMR spectra, shows two kinds observed in the region 6.5ppm of the spectrogram of Fig. 6 A The integration of substance.The amount of transesterification substance is about 42%, and the amount of unreacted DEMM is about 58%.

Fig. 7 be include block isocyanuric acid ester reaction mixture illustrative proton NMR spectra.

Fig. 8 is the illustrative of intermediate glycol¹³C-NMR spectrogram.

Fig. 9 is (a) pure DEMM, (b) DEMM and urethane esterdiol (no sulfuric acid), (c) DEMM, urethanes Two pure and mild sulfuric acid, and DEMM after (d) being reacted 1 hour at 135 DEG C, urethane esterdiol and sulfuric acid it is illustrative¹³C- NMR spectra.

Specific embodiment

Explanation and illustration given herein is intended to make others skilled in the art to be familiar with the present invention, its principle and in fact Border application.Those skilled in the art can adjust in a variety of forms and with the application of the invention, making it that can be most suitable for wanting for special-purpose It asks.Therefore, the specific embodiments of the present invention illustrated are not intended to for exhaustive or limit this introduction.Therefore, this religion The range led should not determine with reference to above description, but should be assigned with reference to appended claims and these claims The full scope of equivalent determines.The disclosure of all articles and bibliography, including patent application and publication, with Way of reference is incorporated to for all purposes.It is also possible for such as combining other obtained from following following claims, described Claim is also incorporated by reference in this written description accordingly.

Unless otherwise defined, all technical terms and scientific terms used herein have disclosure fields The normally understood meaning of technical staff.Many used in the disclosure is provided below with reference to document for those skilled in the art The general definition of term: Singleton et al., Dictionary of Microbiology and Molecular Biology (second edition, 1994)；The Cambridge Dictionary of Science and Technology (Walker is edited, 1988)；The Glossary of Genetics, the 5th edition, R.Rieger et al. (editor), Springer Verlag (1991)；And Hale&Marham, The Harper Collins Dictionary of Biology (1991).

As used herein, acid catalyst is catalyzed transesterification while side reaction being made to minimize or not facilitate side reaction Acidic materials.One or more as used herein means can be as disclosed using at least one of described component Or it is more than one.Nominally refer to theoretical functionality about what degree of functionality used；In general, this can be by the stoichiometry of ingredient used To calculate.Hetero atom refers to and the atom of non-carbon or hydrogen, such as nitrogen, oxygen, sulphur and phosphorus；Hetero atom may include nitrogen and oxygen.As herein Used, alkyl refers to containing the group of one or more atoms backbones and hydrogen atom, optionally contains one or more Hetero atom.When alkyl contains hetero atom, hetero atom can form one or more functional groups well-known to those having ordinary skill in the art. Any combination of alkyl containing alicyclic, aliphatic, aromatics or these sections.Aliphatic section can be linear chain or branched chain.Rouge Race and alicyclic section may include one or more double bonds and/or three keys.Alkyl, alkenyl, alkynyl, aryl, naphthenic base, cyclenes Base, alkaryl and aralkyl are included in alkyl.Alicyclic group can contain annulus and acyclic moiety.Alkylene refers to Alkyl or any subset with more than one chemical valence, such as alkylidene, alkenylene, alkynylene, arlydene, sub- cycloalkanes Base, sub- cycloalkenyl, alkarylene and sub- aralkyl.Unless otherwise specified, weight % used herein or parts by weight refer to Or the weight based on the compound or composition.Unless otherwise stated, parts by weight are compositions related based on 100 parts.

Be functionalized polyol include the central part formed by polyol, wherein one in hydroxyl or It is multiple to be reacted with functional compound so that polyol is functionalized.Polyol can be with two or more The monomeric compound of hydroxyl, be also possible to include two or more hydroxyls polymerizable compound.It is functionalized polyol Preferably include the functional group different from the structure along center section lengths.Preferably, functionalization polyol includes alkenyl. For example, functional compound can be 1,1-, bis- substitution -1- alkene.Central part usually has two or more ends.Center At least one partial end is preferably attached to functional compound.Preferably, two or more or all ends of central part End is connected to central compound.It should be appreciated that the residue of polyol is connected to when hydroxyl is reacted with functional compound Functionalized compounds.

When polyol is polymer, central part is centre polymer part.

Functionalized polymeric includes the centre polymer part with two or more ends.Centre polymer part At least one end is connected to the functional compound with one or more functional groups.Functional compound preferably includes and along center The different functional group of the structure of polymer moieties length.Preferably, functional compound includes alkenyl.For example, functional compound can To be bis- substitution -1- alkene of 1,1-.

Functionalization polyol (for example, functionalized polymeric) preferably includes two or more alkenyls.Preferably, Two or more alkenyls include the first alkenyl being spaced apart with the second alkenyl.For example, alkenyl can be predominantly located at functionalization polymerization On the end compound (for example, terminal monomeric) of object.

Functionalization polyol (for example, functionalized polymeric) can pass through the polyhydroxy with end or pendant hydroxyl group It is prepared by the reaction of compound (for example, polyalcohol) and 1,1- disubstituted olefin.For example, reaction may include ester exchange reaction.It should Reaction can block the one or more of polyol (for example, polyalcohol), two with 1,1- disubstituted olefin compound Or more or all ends.

The preferred long enough of polyol, allow hydroxyl respectively easily with functionalization according to the teaching of this article Close object reaction.For example, the oxygen atom of hydroxyl can by about 5 or more other atoms, more preferably from about 7 or more it is another Outer atom, more preferably from about 9 or more other atomic separations are opened.

In all fields, polyol, which can provide, requires polyol to deposit as oligomeric compound or polymer Mechanically or physically characteristic (for example, flexibility, low-temperature impact resistance, ductility or any combination of them).Therefore, polyhydroxy The interval between hydroxyl on based compound can be about 12 or more, about 20 or more, about 50 or more or about 100 or more It is more.

Polyol is preferably short enough, so that polyol has the functional group of high concentration.For example, divide equally again Son amount and the ratio of the terminal hydroxyl number of per molecule (for example, each polymer molecule) are about 200,000 or smaller, more preferably It is about 100,000 or smaller, is even more preferably about 40,000 or smaller, is even more preferably about 10,000 or smaller, Most preferably about 4,000 or smaller.

Monomer polyol

Polyol can be the monomeric compound with two or more hydroxyls spaced apart.Monomer polyhydroxy Compound can be straight chain compound or straight chain compound.

The example of branch polyol includes neopentyl glycol, pentaerythrite, methyl substituted propylene glycol, ethyl substitution Propylene glycol, methyl, ethyl, propyl replace butanediol, methyl, dimethyl, trimethyl, ethyl, diethyl, triethyl group, third The hexylene glycol etc. that base, dipropyl replace.For example, branch polyol includes 2- methyl-1,3-propanediol, 3- methyl-1, 5- pentanediol, neopentyl glycol, 2,2- diethyl -1,3- propylene glycol, 2-butyl-2-ethyl-1,3-propanediol, 2,2- diethyl - 1,3- propylene glycol, 2-butyl-2-ethyl-1,3-propanediol, 2- methyl-1,8- ethohexadiol, 2,2,4- trimethyl -1,3- penta 2 Alcohol, 2- ethyl -1,3- hexylene glycol, 1,4 cyclohexane dimethanol or any combination of them.Branch polyol other Example will be obvious to those of ordinary skill in the art.

Straight chain polyol includes the hydrocarbyl chain without branch.The example of such compound include 1,5- pentanediol, 1,6-HD, 1,7- heptandiol, 1,8- ethohexadiol, 1,9- nonanediol, 1,10- decanediol, 1,12- dodecanediol, 1,13- Tridecane diols, diethylene glycol (DEG), triethylene glycol, tetraethylene glycol, 1,4 cyclohexane dimethanol, 1,5- decahydronaphthalene glycol etc..Preferred straight chain Polyalcohol is 1,6-HD, 1,8- ethohexadiol, 1,10- decanediol, 1,12- dodecanediol, tetraethylene glycol and theirs is mixed Close object.

Other examples of polyol include the compound with one or more nitrogen-atoms.Including the excellent of nitrogen-atoms Selecting polyol includes one or more cyanurate groups, such as isocyanurate group.Polyol includes Three (hydroxyalkyl) isocyanuric acid esters, three (hydroxyphenylmethyl) cyanurates.For example, polyol may include 1,3,5- tri- (2- ethoxy) isocyanuric acid ester.

Centre polymer part

Centre polymer part, which can be, to be substantially made of a kind of monomeric compound or completely by a kind of monomeric compound The homopolymer of composition, or the copolymer including two or more different monomers compounds.The example of copolymer includes alternating Copolymer, random copolymer and block copolymer.

Centre polymer part preferably has by the repetitive unit of 1 or 2 monomer composition.

Centre polymer part preferably includes one or more polyalcohols, be substantially made of one or more polyalcohols or Person is made of one or more polyalcohols completely.Any polyalcohol can be used, precondition is polyalcohol at the end of polymer chain End includes one or more or two or more hydroxyls along the length of polymer chain.Preferred polyalcohol include polyester, Polyethers, polybutadiene polyol, polycarbonate, polyacrylate (e.g., including acrylic acid and/or methacrylic acid).

Centre polymer part can have main chain, the covalent bonding as needed for the end of connection centre polymer part Atom limits.The atom of main chain does not usually include side group, unless they connect with other monomeric unit, such as has 2 Or more in the polymer of the long chain branches of monomeric unit.

As used herein, monomeric compound refers to the chemical structure of molecule, and monomeric unit refers to individual molecule.Example Such as, the first monomeric unit and second comonomer can refer to the molecule with identical or different chemical structure.Similarly, the first singulation It closes object and second comonomer compound refers to the molecule with different chemical structures.

Alternating copolymerization monomer can be substantially by alternately arranged first monomeric compound (for example, R1-M¹- R2) and second Monomeric compound is (for example, R3-M²- R4) composition.Herein, centre polymer part (P¹) can be described as including single by one kind first The repetitive unit (for example, A) or be substantially made of the repetitive unit that body compound and a kind of second comonomer compound are formed:

P¹=R1- (A)_n- R4,

Wherein A=-M¹–M², n is at least 3, and at least one of R1 and R4 can be reacted with functionalized compounds with Functional group (a preferably at least alkenyl) is added to the end of centre polymer part.R1 or R4 is preferably subjected to transesterification, and It is highly preferred that R1 and R4 undergo transesterification.

First monomer can be centre polymer part (P²) both ends terminal monomeric:

P²=R1- (A)_n–M¹- R2,

Wherein A=-M¹–M², n is at least 3, and at least one of R1 and R2 can be reacted with functionalized compounds with Functional group (a preferably at least alkenyl) is added to the end of centre polymer part.R1 or R2 is preferably subjected to transesterification, and It is highly preferred that R1 and R2 undergo transesterification.

The repetitive unit of centre polymer part can chemical structure having the same, can also have two or more difference Chemical structure.

Monomeric compound or the repetitive unit of centre polymer part may include aliphatic group, aromatic group or both.Virtue Race's group can be located on main chain, can also be used as side group presence.Aliphatic group can be located on main chain, can also be used as side group and deposit ?.

Condensation reaction (for example, polycondensation reaction) can be used to be formed by one or more monomers for centre polymer part.For example, Condensation can be reacting between the alcohol radical of the first monomeric unit and the acidic group (for example, carboxyl-CO (OH)) of second comonomer unit, Form ester bond in the reaction to connect two monomeric units.

Centre polymer part may include the ester bond for connecting adjacent repeat unit, and centre polymer part may include connection weight The ester bond of the monomeric unit of multiple unit, or both.

Centre polymer part can at least be formed by following monomeric compound:

(HO-M³- O (OH) C, with alcohol radical and carboxylic acid group, so that centre polymer part includes repetitive unit: M³.In Heart polymer moieties may include repetitive unit M³, it is consisting essentially of or be made from it completely.

Centre polymer part can be formed by the ring-opening polymerisation of one or more monomeric compounds.

Centre polymer part can pass through at least the first monomeric compound (glycol) and second comonomer compound (diacid) Polycondensation reaction is formed.All glycol can be identical, or can be two or more different diol monomer compounds.It is all Diacid can be identical, or can be two or more different diacid monomer compounds.Polycondensation reaction preferably results in moisture The generation of son.Centre polymer part can be prepared with excessive glycol, so that each end of centre polymer part has Hydroxyl.Preferably, each end of centre polymer part has hydroxyl.It is highly preferred that each end of centre polymer part End has hydroxyl (for example, on end monomer unit).Preferably, hydroxyl is reacted with functionalized compounds to form ester bond.

Preferably, functionalized polymeric includes one or more functional compounds (Z), and the functional compound passes through ester It is keyed to the end of centre polymer part (P), as below for shown in the centre polymer part with two ends:

Z–C(O)–O–P–O–C(O)–Z。

Preferably, centre polymer part is saturation.Any alkenyl on functionalized polymeric is preferably located in only one kind Or on a variety of functional compounds, the functional compound is all connected to the different ends of centre polymer part.

Polyalcohol

Functionalized polymeric is preferably by making polyalcohol (that is, can be used for the functional hydroxy groups of reaction with two or more The compound of (that is,-OH group)) it reacts and is formed.Hydroxyl may be preferably used for organic reaction.Preferably, hydroxyl include end or Pendant hydroxyl group is substantially made of end or pendant hydroxyl group.

Polyalcohol can be monomer, oligomer or polymer.

Monomeric polyols are usually the low molecular weight compound with about 2 or more hydroxyls.Preferred monomeric polycarboxylic The molecular weight of alcohol is about 400 grams/mol or smaller, more preferably about 300 grams/mol or smaller, most preferably about 250 Gram/mol or it is smaller.Two or more hydroxyls of monomeric diol are preferably spaced sufficiently apart so that they be not together with glycol, It is not vicinal diamines.Preferred monomeric polyols include glycerol, pentaerythrite, antierythrite, ethylene glycol, sucrose, resorcinol, 1, It is 4- butanediol, 1,6-HD, glycerine, bisphenol-A, 4,4'- dihydroxyl dicyclohexyl, 1,4- pentanediol, 1,5- pentanediol, sweet Reveal alcohol, D-sorbite, 2,5- tetrahydrofuran-dimethanol and 1,2,6- hexanetriol.

Polyester polyol

Centre polymer part may include polyester polyol, can be homopolymer or copolymer.Polyester homopolymer and altogether Polymers, the monomer for being used to prepare polyester and the example for being used to prepare the method for polyester that can be used for centre polymer part include Polymer described in following United States Patent (USP): the No.4,725,664 of Halmess et al. is (see, for example, the 15th row of the 3rd column to the 6th The 41st row of column), No.2,973,339, Hrach of No.4,067,850, Muenster of Kohler et al. et al. et al. The No.4,377,682 of No.3,651,016, Ohguchi et al.；The No.3,972,852 of Inata et al.；Login's et al. No.9,309,345 and Hoshino of No.5,700,882, Hickey of No.4,263,370, Jones et al. et al. et al. No.8,318,893, these patents are herein incorporated by reference.

Polyester polyol may include one or more repetitive unit features of following polymer: polyglycolide is (that is, poly- (oxygen (1- oxo -1,2- second diyl), such as the condensation from glycolic)；Polylactic acid (for example, open loop from lactide) is gathered Acid lactone (for example, the open loop for carrying out caprolactone), polyhydroxyalkanoatefrom (for example, poly butyric ester), gathers oneself at polycaprolactone Naphthalate, PHBV (that is, copolymer of 3-hydroxybutyrate and 3- hydroxypentanoic acid, butyrolactone and valerolactone), poly-succinic Butanediol ester (for example, condensation from succinic acid and 1,4-butanediol), polyethylene terephthalate (for example, from pair Phthalic acid and ethylene glycol), it is polybutylene terephthalate (PBT) (for example, from terephthalic acid (TPA) and Isosorbide-5-Nitrae butanediol), poly- to benzene Naphthalate (PTT) (for example, condensation from terephthalic acid (TPA) and 1,3-PD) and poly- naphthalenedicarboxylic acid ethylene glycol Ester (PEN) (for example, condensation from least one naphthalenedicarboxylic acid and ethylene glycol).Workable another kind polyester is by 4- hydroxyl Benzoic acid 6- hydroxyl naphthalene -2- carboxylic acid is condensed the polymer to be formed.Polyester may include aliphatic dicarboxylic acid and/or aliphatic diol.

Polyester can be aromatic polyester.Aromatic polyester can be formed and making Aromatic Acid Component with hydroxylating component reaction.

The Aromatic Acid Component of aromatic polyester polyols composition can be such as O-phthalic acidic base materials, O-phthalic Acid, terephthalic acid (TPA), M-phthalic acid, phthalic anhydride, benzenetetrahydride, dimethyl terephthalate (DMT), poly- terephthaldehyde Sour glycol ester, trimellitic anhydride, tower bottoms, their derivative and their combination.O-phthalic used herein Acidic base materials refer to the derivative of phthalic acid or phthalic acid.The example of O-phthalic acidic base materials includes for example various Phthalic acid, such as terephthalic acid (TPA) and M-phthalic acid, dimethyl terephthalate (DMT), gather to benzene two phthalic anhydride Formic acid glycol ester, trimellitic anhydride, their derivative and their combination.It is used to prepare the adjacent benzene two of polyester polyol Formic acid sill can be (a) substantially pure phthalic acid or phthalic acid derivatives, such as phthalic anhydride, right Phthalic acid, dimethyl terephthalate (DMT), M-phthalic acid and trimellitic anhydride；Or (b) some complicated mixtures, such as Effluent, waste or waste products containing phthalic acid residue.In this context, " phthalic acid residue ", which refers to, is making The standby rear method by wherein phthalic acid or derivatives thereof as starting ingredient (including tower bottoms) retains in the product Any reaction or unreacted phthalic acid.The complex mixture of phthalic acid residue in United States Patent (USP) No.5, It is further described in 922,779, which is herein incorporated by reference.

The preferred O-phthalic acidic base materials for being used to prepare aromatic polyester polyols are phthalic anhydrides.The component can be with With phthalic acid or phthalic anhydride tower bottom composition, the thick composition of phthalic anhydride or phthalic anhydride light fraction Composition replaces, such as United States Patent (USP) No.4, this kind of composition defined in 529,744.

The Aromatic Acid Component of aromatic polyester polyols composition can account for about 20 weights of such as aromatic polyester polyols composition Measure % to about 50 weight %, or about 20 weight % to about 40 weight %.

The hydroxylating component of the aromatic polyester polyols composition of this technology can be for example, at least a kind of aliphatic diol, its At least one derivative or their combination

Hydroxylating component can be the aliphatic diol of following general formula

(1): HO-R¹—OH

Wherein R¹For the bivalent group selected from the group being made up of: (a) alkylidene containing 2 to 6 carbon atoms, with And (b) group of following formula:

(2) :-(R²O)_n—R²—

Wherein R²For the alkylidene containing 2 to 3 carbon atoms, n is integer of 1 to 3, and (c) their mixture.

The example of suitable formula (1) aliphatic diol includes ethylene glycol, propylene glycol, diethylene glycol (DEG), dipropylene glycol, propylene glycol, fourth Glycol, 1,2- cyclohexanediol, poly- (oxyalkylene) polyalcohol, they contain two to four by ethylene oxide, propylene oxide or it Any combination etc. condensation derived from alkylidene.As understood by those skilled in the art, in the poly- (oxygen of mixing Ethylene-oxypropylene) polyalcohol preparation in, ethylene oxide and propylene oxide can add hydroxyl in the form of filling material or sequentially Initial reactant in.If desired, the mixture of such glycol can be used.Currently most preferably formula (I) aliphatic diol is two Glycol.In addition, amine-based aliphatic hydroxylated materials (that is, hydroxylated amine) can be used, such as monoethanolamine, diethanol amine and three ethyl alcohol Amine, as long as all amine functional groups completely consume in polyalcohol.

The mixture of glycol may include low molecular weight polyols (that is, per molecule contains less than 7 carbon atoms but per molecule contains Have the compound of at least three hydroxyls), amount is usually total hydroxylated materials greater than 0 to 100%.Such polyalcohol includes example As glycerol, 1,1,1- trimethylolpropane, 1,1,1- trimethylolethane, 2,2- dimethyl -1,3- propylene glycol, pentaerythrite, Their mixture etc..

The hydroxylating component of aromatic polyester polyols composition can be such as diethylene glycol (DEG), glycerol, trimethylolpropane, season Penta tetrol, ethylene glycol, propylene glycol, dipropylene glycol, propylene glycol, butanediol, 1,2- cyclohexanediol, hexylene glycol, pentanediol, polyoxygenated Enediol (for example, triethylene glycol and tetraethylene glycol), their derivative and their combination.

Based on the total weight of aromatic polyester polyols composition, the hydroxylating component of aromatic polyester polyols composition can be accounted for For example, about 30% to about 80%.Alternatively, the total weight based on polyester polyol, the hydroxylating component of aromatic polyester polyols can be About 30 weight %-65 weight %.The hydroxylated materials alternatively, total weight based on aromatic polyester polyols, in polyester polyol It is about 40 weight %-60 weight %.

Polyester may include one or more Isosorbide-5-Nitrae-arylene monomers such as terephthalic acid (TPA)s and quinhydrones or 2,6- arylene monomers Such as 2,6- dihydroxy naphthlene, reacted with straight chain and non-branched aliphatic diacid or glycol, the straight chain and non-branched aliphatic series two The functional group of acid or glycol is by the functional group reactions with arylene monomers.Polyester of the invention can be by diacid and glycol via ester The condensation of exchange and prepare, the transesterification such as hydroquinone diacetate or 2, the ester of 6- naphthalene diacetate esters and aliphatic diacid is handed over It changes.Polyester of the invention is usually prepared in the following manner: the ester of dimethyl terephthalate ester and linear saturation aliphatic diol Exchange；The transesterification of hydroquinone diacetate and linear saturation aliphatic diacid, with the direct esterification of linear saturation aliphatic diacid, to benzene Dimethyl chloride and the esterification of the non-branched saturated diols of straight chain, the transesterification of 2,6- naphthalene diacetate esters and the non-branched glycol of linear saturation Reaction and the esterification for using foregoing dicyclohexylcarbodiimide (DCC), diacid and glycol.Alkyl be tool there are four or The low alkyl group of less carbon.In reaction below, any carboxylic acid halides can be used to replace acyl chlorides, propionate or butyrate can be used (there are four tools or the low alkyl group of less carbon atom) replaces acetate.In this aspect of the invention, polyester may be defined as polymerizeing The reaction product of object carrier, wherein polyester is the Asia selected from the group by quinhydrones, 2,6- hydroxyl naphthalene and their mixture composition Aryl monomer and the linear saturation aliphatic diol with 6 to 17 carbon atoms or the reaction product of diacid, the glycol or diacid It can be reacted with arylene monomers, and wherein R=alkyl with 1 to 4 carbon atoms or H, R'=have 1 to 4 carbon atom Alkyl, and X=halogen.

Polyester polyol can regularly replace between aromatic substituent and the non-branched substituent group of straight chain, and the straight chain is non- Branched alkyl substituent separates or interval arlydene.It is small number of as the interval between arlydene increases to increase total molecular weight The class liquid crystal characteristic of repetitive unit meeting reinforced polyester, will usually have about 350 to about 4,000, preferably from about 400 to about 1800 Number-average molecular weight in range.The degree of polymerization can be controlled by the relative scale of monomer in reaction.

Polyhydroxy component can be selected based on the desired characteristic of glycol composition, to be used to prepare polyester polyol.It can make With any suitable polyol；For example, polyol can be dihydroxy compounds (glycol), trihydroxy chemical combination Object (triol), tetrahydroxy compound (tetrol) or more advanced polyol.More particularly, polyol can be with Be ethylene glycol, diethylene glycol (DEG), polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butanediol, pentanediol, hexylene glycol, glycerol, Trimethylolpropane, pentaerythrite or D-sorbite or their combination.

Polybasic carboxylic acid may is that the polybasic carboxylic acids or corresponding ester or acid anhydrides of diacid, three acid or higher functionality, including but It is not limited to multifunctional aromatic acid, multifunctional aromatic anhydride and multifunctional aromatic ester (for example, diol monoester) and multifunctional aliphatic series Acid, acid anhydrides and its multifunctional ester, such as succinic acid, glutaric acid, adipic acid, phthalic acid, terephthalic acid (TPA), decanedioic acid, nonyl Diacid, dodecanedioic acid, citric acid, succinic anhydride, phthalic anhydride, dimethyl succinate, dimethyl glutarate, adipic acid Dimethyl ester, dimethyl terephthalate (DMT) and their combination.

Hydrophobic material can be vegetable oil (that is, oil of plant origin), or fatty acid or ester as derived from it；Animal oil (that is, oil of animal origin), or fatty acid or ester as derived from it；Or synthetic oil, synthetic fatty acid or Acrawax. So-called oil refers to hydrophobic compound, the physical state regardless of it at room temperature；That is, oil can be solid, example at room temperature Such as hard fat.

Polyester polyol may include multifunctional aromatic acid or its acid anhydrides or its Acibenzolar or its multifunctional ester or it is mixed Close object.For example, polyester polyol may include terephthalic acid (TPA), M-phthalic acid, phthalic acid, trimellitic acid, equal benzene tetramethyl Acid or any combination of them.

Polycarbonate polyol

Centre polymer part can be formed by polycarbonate polyol.Polycarbonate polyol can be including with carbon The repetitive unit of acid esters group (that is,-O-C (=O)-O-) is substantially made of the repetitive unit or completely single by the repetition Any polymer of member composition.Polycarbonate polyol includes two or more hydroxyls (for example, two or more end hydroxyls Base).Polycarbonate polyol may include polycarbonate glycol, polycarbonate triol, the poly- carbon with four or more hydroxyls Acid esters polyalcohol or any combination of them.Polycarbonate polyol can be straight chain.Preferred Linear polycarbonate polyalcohol There is hydroxyl in each end.Polycarbonate polyol can be branch or over-expense chain polymerization with three or more ends Object.Preferably, branch or overspend chain polycarbonate polyol two or more, three or more or even all ends End includes hydroxyl.

The example of polycarbonate polyol and the method for being used to prepare polycarbonate polyol includes United States Patent (USP) No.3, 689,462 A (being announced by Maximovich on September 5th, 1972, see, for example, the 25th row of the 1st column to the 35th row of the 8th column), 4, 533,729 (being announced by Newland et al. on August 6th, 1985, see, for example, the 54th row of the 1st column to the 53rd row of the 4th column), US 5,288,839 A (being announced by Greco on 2 22nd, 1994, see, for example, the 12nd row of the 2nd column to the 2nd row of the 5th column), US 5, 527,879 A (are issued by Nakae et al. on June 18th, 1996, see, for example, abstract of description and the 9th row of the 2nd column to the 3rd The 48th row of column), US 6,872,797 B2 (issue by Ueno et al. on March 29th, 2005, extremely see, for example, the 44th row of the 5th column The 65th row of 16th column and the 20th row of the 19th column are to the 55th row of the 24th column) and 8,779,040 B2 of US (by van der Weele Et al. issued on July 15th, 2014, see, for example, the 12nd row of the 5th column to the 32nd row of the 15th column) and U.S. Patent application it is public 2003/0176622 A1 of cloth US (by Konishi on September 18th, 2003 announce, see, for example, paragraph 8-74), US20040092699 A1 (is announced by Ueno et al. on May 13rd, 2004, see, for example, abstract of description, paragraph 2-8,13- 37 and 39-151), US2008/0146766 A1 (announces by Masubuchi et al. on June 19th, 2008, see, for example, explanation Book extract and paragraph 13-54) and US20080167430A1 (announced by Bruchmann et al. on July 10th, 2008, referring to example As described in paragraph 3-149) those, the content of these documents is herein incorporated by reference.

Polycarbonate polyol can be homopolymer or copolymer.Polycarbonate polyol may include the repetitive structure of following formula Carbonate unit (can be identical or different), substantially by the repetitive structure carbonate unit or completely by the repetitive structure carbon Acid esters unit composition:

Wherein R¹Group is preferably aliphatic, alicyclic, aromatics or any combination of them.Preferably, R¹Group sum At least about 60% is aromatic organic radicals, remaining is aliphatic, alicyclic or aromatic group.In one aspect, each R¹For aromatics Organic group, such as the group of following formula :-A¹-Y¹-A², wherein A¹And A²Each of be monocyclic divalent aryl, and Y' is With by A¹With A²The bridge linkage group of one or two separated atom.For example, an atom is by A¹With A²It separates.This kind of group Exemplary, non-limiting example be-O-,-S-,-S (O)-,-S (O2)-,-C (O)-, methylene, cyclohexyl be sub- Methyl, 2- [2.2.1]-bicycloheptylidene, ethylidene, isopropylidene, neopentylidene, cyclohexylidene, sub- cyclopentadecane base, sub- ring Dodecyl and adamantyl.Bridge linkage group Y' can be alkyl or saturated hydrocarbyl, such as methylene, cyclohexylidene or different sub- third Base.

Polycarbonate can be by with formula HO-R¹Prepared by the interfacial reaction of the dihydroxy compounds of-OH, wherein R¹As above It is defined.Dihydroxy compounds suitable for interfacial reaction includes the dihydroxy compounds and formula HO-A of formula (A)¹-Y¹-A²-OH Dihydroxy compounds, wherein Y1, A¹And A²As described above.Further include the bisphenol compound of following general formula:

Wherein R^aAnd R^bRespectively indicate halogen atom or univalence hydrocarbyl, and can be identical or different；P and q are each independently For 0 to 4 integer；And X^aIndicate one of the group of following formula:

Wherein R^cAnd R^dEach independently represent hydrogen atom or monovalent straight chain or cyclic hydrocarbon group, and R^eFor bivalent hydrocarbon radical.

Some Exemplary, non-limiting examples of suitable dihydroxy compounds include: resorcinol, quinhydrones, 4,4'- bis- Xenol, 1,6- dihydroxy naphthlene, 2,6- dihydroxy naphthlene, bis- (4- hydroxy phenyl) methane, bis- (4- hydroxy phenyl) diphenylmethyls Alkane, bis- (4- hydroxy phenyl) -1- naphthyl methanes, bis- (4- hydroxy phenyl) ethane of 1,2-, bis- (4- the hydroxy phenyl) -1- phenyl of 1,1- Ethane, 2- (4- hydroxy phenyl) -2- (3- hydroxy phenyl) propane, bis- (4- hydroxy phenyl) phenylmethanes, the bis- (hydroxy benzenes of 1,1- Base) pentamethylene, 1,1-bis(4-hydroxyphenyl)-cyclohexane, bis- (4- hydroxy phenyl) isobutenes of 1,1-, bis- (the 4- hydroxy benzenes of 1,1- Base) cyclododecane, bis- (4- the hydroxy phenyl) -2- butylene of trans- -2,3-, bis- (4- hydroxy phenyl) adamantane of 2,2-, (α, α '-it is bis- (4- hydroxy phenyl) toluene, bis- (4- hydroxy phenyl) acetonitriles, 2,2-bis(3-methyl-4-hydroxyphenyl) propane, bis- (the 3- second of 2,2- Base -4- hydroxy phenyl) propane, bis- (3- n-propyl -4- hydroxy phenyl) propane of 2,2-, the bis- (3- isopropyl -4- hydroxy benzenes of 2,2- Base) propane, bis- (3- sec-butyl -4- hydroxy phenyl) propane of 2,2-, 2,2- bis- (3- tert-butyl-hydroxy phenyl) propane, 2,2- Bis- (3- allyl -4- hydroxy phenyl) propane of bis- (3- cyclohexyl -4- hydroxy phenyl) propane, 2,2-, bis- (the 3- methoxyl groups-of 2,2- 4- hydroxy phenyl) propane, 4,4'- dihydroxy benzophenone, bis- (4- the hydroxy phenyl) -2- butanone of 3,3-, bis- (the 4- hydroxy benzenes of 1,6- Base) -1,6- acetyl butyryl, bis- (4- hydroxy phenyl) ethers of ethylene glycol, bis- (4- hydroxy phenyl) ethers, bis- (4- hydroxy phenyl) sulfide, Bis- (4- hydroxy phenyl) sulfoxides, bis- (4- hydroxy phenyl) sulfones, bis- (4- hydroxy phenyl) fluorine of 9,9-, 2,7- dihydroxy pyrene, 6,6'- bis- Hydroxyl -3,3,3 ', 3 '-tetramethyl spiral shell (double) dihydroindene (" spirobindene bis-phenol "), bis- (4- hydroxy phenyl) phthalides of 3,3-, 2- benzene Bis- (4- hydroxy phenyl) phthalimidines (PPPBP) of base -3,3-, 2,6- dihydroxy dibenzo-are to dioxin, 2,6- dihydroxy thiophene Anthracene, 2,7- dihydroxy phenoxthine, 2,7- dihydroxy -9,10- dimethylphenazine, 3,6- dihydroxy dibenzofurans, 3,6- dihydroxy Base dibenzothiophenes and 2,7- dihydroxy carbazole etc., and the combination comprising at least one of aforementioned dihydroxy compounds.

The specific example for the bisphenol compound type that can be indicated by formula (3) includes 1,1- bis- (4- hydroxy phenyl) methane, 1, Bis- (4- hydroxy phenyl) propane (referred to hereinafter as " bisphenol-A " or " BPA ") of bis- (4- hydroxy phenyl) ethane of 1-, 2,2-, the bis- (4- of 2,2- Hydroxy phenyl) butane, bis- (4- hydroxy phenyl) octanes of 2,2-, bis- (4- hydroxy phenyl) propane of 1,1-, bis- (the 4- hydroxy benzenes of 1,1- Base) normal butane, bis- (4- hydroxyl -1- aminomethyl phenyl) propane of 2,2- and bis- (the 4- hydroxy-tert-butyl phenyl) propane of 1,1-.It can also make With the combination comprising at least one of aforementioned dihydroxy compounds.

Polycarbonate can be Linear polycarbonate or branched polycarbonate.Branched polycarbonate can be by during polymerization Branching agent is added to prepare.These branching agents include the multifunctional organic compound containing at least three functional groups, the function Group is preferably chosen from the mixture of hydroxyl, carboxyl, carboxylic acid anhydrides, haloformyl and aforementioned functional groups.Based on the total of polycarbonate Weight, the additive amount of branching agent can be about 0.05 weight % or more, it is therefore preferable to about 0.10 weight % or more.Branching agent Amount can be about 10 weight % or less, it is therefore preferable to about 2 weight % or less.Imagine all types of polycarbonate terminal groups all may be used For in polycarbonate compositions, precondition to be the desired characteristic that these end groups are not significantly affected by thermoplastic.

Suitable polycarbonate can be prepared by the method for such as interfacial polymerization and melt polymerization.Although interfacial polymerization is anti- Answer condition that can change, but illustrative methods generally include dihydric phenol reactant being dissolved or dispersed in aqueous caustic soda or causticity In potassium, gained mixture is added in suitable solvent medium unmixing with water, and in controlled pH condition such as from about 8 to about Under 10, contact reactant with carbonate precursor in the presence of suitable catalyst such as triethylamine or phase transfer catalyst.Most Common solvent unmixing with water includes methylene chloride, 1,2- dichloroethanes, chlorobenzene, toluene etc..Suitable carbonate precursor Double haloformates including such as carbonyl halide such as carbonyl bromide or phosgene or haloformate such as dihydric phenol are (for example, bisphenol-A Bischloroformates, quinhydrones etc.) or glycol double haloformates (for example, ethylene glycol, neopentyl glycol, polyethylene glycol etc. is double Haloformate).The combination of at least one of carbonate precursor comprising aforementioned type can also be used.

Polycarbonate glycol as used herein and polycarbonate polyol further include the copolymerization comprising carbonate chain units Object.Copolycarbonate may include carbonate chain units, substantially be made of carbonate chain units or completely by carbonic ester Chain element composition.Copolycarbonate can also comprise the repetitive unit of one or more non-carbonic esters.For example, polycarbonate Copolymer may include polyester, such as in the form of copolyesters-polycarbonate.This analog copolymer may include the repetitive unit of following formula:

Wherein D is the bivalent group derived from dihydroxy compounds, and can be such as C_2-10Alkylidene, C_6-20Alicyclic ring Race's group, C_6-20Aromatic group or polyalkylene oxide groups, wherein alkylidene contains 2 to about 6 carbon atoms, and specifically 2,3 or 4 A carbon atom；And T is the bivalent group derived from dicarboxylic acids, and can be such as C_2-10Alkylidene, C_6-20Alicyclic group Group, C_6-20Alkyl aromatic group or C_6-20Aromatic group.

Diene polyol

Polyalcohol may include one or more diene polyols, be substantially made of one or more diene polyols or It is made of completely one or more diene polyols.Diene polyol preferably includes one or more diene, in an amount of from about 40 weights Measure % or more, more preferably about 70 weight % or more, and most preferably about 90 weight % or more.Diene is preferred Ground be with about 4 to about 20 carbon atoms, more preferably from about 4 to about 8 carbon atoms, most preferably 4 carbon atoms diene.

Particularly preferred diene polyol is polybutadiene polyol.Polybutadiene polyol preferably includes about 40 weight % Or more butadiene repeat units.Butadiene can be used as 1-2 addition, cis- 1-4 addition, 1-4 trans-addition or they Any combination exists.Sum based on butadiene repeat units in polyalcohol, it is preferable that the amount of 1-2 addition is about 50% or more It is small, more preferably about 40% or smaller, most preferably about 30% or smaller.

The polyalkylsiloxane of methanol sealing end

Centre polymer part may include the polyalkylsiloxane of methanol sealing end.Preferred polyalkylsiloxane is in each silicon There is one or preferably two alkyl on atom.Preferred alkyl is C₁-C₁₀Hydrocarbon.It is highly preferred that alkyl include ethylene or completely It is made of ethylene.Particularly preferred polyalkylsiloxane is dimethyl silicone polymer.Polyalkylsiloxane can be straight chain or branch Chain.Preferably, each end of the chain includes hydroxyl.

Polyalkylene glycol

Centre polymer part may include polyalkylene glycol.Polyalkylene glycol preferably includes have 2 to 10 carbon originals The aklylene glycol of son is substantially made of the aklylene glycol or is made of completely the aklylene glycol.Preferably, C_2- C₁₀The amount of aklylene glycol is about 50 weight % or more, more preferably about 80 weight % or more, even more preferably for About 90 weight % or more, and most preferably about 95 weight % or more.Polyalkylene glycol may include straight chain polymer, Branched polymer or both.Preferably, polyalkylene glycol includes hydroxyl in each end of polymer.Branched polymer can have There are 3,4,5,6,7 or more the end of the chains.Super branched polymer can have about 8 end of the chains or more, about 15 chains End or more or about 20 end of the chains or more.

Preferred polyalkylene glycol includes ethylene glycol, butanediol, propylene glycol or any combination of them.Based on poly- alkylene The total weight of base glycol, the total amount of ethylene glycol, propylene glycol or butanediol are preferably about 50 weight % or more, more preferably About 85 weight % or more are even more preferably about 92 weight % or more, most preferably about 97 weight % or more.

Central part may include the ethoxylate with two or more hydroxyls.For example, ethoxylate can be The ethoxylate of aliphatic compounds or aromatic compounds.Ethoxylate may include any amount of ethylene oxide group.It is excellent Selection of land includes one or more ethylene oxide groups for each '-hydroxyethoxy glycolylate.Ethoxylate can be straight chain Object is closed, branch is also possible to.The example of branched chain ethoxylates is glycerol ethoxylate.

Centre polymer part may include cyclic polyols.Cyclic polyols preferably include the N-C=O ring as main chain Shape structure and one or more hydroxyl, preferably 3 ethyl hydroxies, are substantially made of them or are made of completely them.Ring The example of shape polyalcohol is 1,3,5- tri- (2- ethoxy) isocyanuric acid ester.

Functional compound

Disclosed composition includes 1,1-, bis- substitution -1- olefin(e) compound, is preferably the alkene that 1,1 dicarbapentaborane replaces Hydrocarbon compound.The olefin(e) compound that preferred 1,1 dicarbapentaborane replaces is the vinyl compound that 1,1- dicarbapentaborane replaces.Bis- carbonyl of 1,1- The vinyl compound that base replaces refers to the change for double key carbon connected to it and being further bonded to two carbonylic carbon atoms Close object.Exemplary compounds are as shown in Equation 1:

Wherein R is that can contain one or more heteroatomic alkyl, and X is oxygen or direct key (for example, methylene β -one Ester).The ethylene that the other 1,1- dicarbapentaborane of exemplary class replaces is methylene malonate, methylene 'beta '-ketoester or diketone.Methylene Phenyl malonic ester is as illustrated in formula 2:

R can be respectively alkyl, alkenyl, C in each appearance₃-C₉Naphthenic base, heterocycle, alkyl heterocyclic, aryl, aralkyl Base, alkaryl, heteroaryl or alkane heteroaryl or polyoxyalkylene or two R form 5-7 member ring-type or heterocycle.R is in each appearance It can be respectively C₁-C₁₅Alkyl, C₂-C₁₅Alkenyl, C₃-C₉Naphthenic base, C_2-20Heterocycle, C_3-20Alkane heterocycle, C_6-C₁₈Aryl, C_7- C₂₅Alkaryl, C_7-25Aralkyl, C_5-18Heteroaryl or C_6-25Miscellaneous alkyl aryl or polyoxyalkylene or two R form 5-7 member ring Shape or heterocycle.Cited group can be substituted by one or more substituents, these substituent groups will not interfere disclosed herein Reaction.Preferred substituent group include halogenated alkylthio, alkoxy, hydroxyl, nitro, azido, cyano, acyloxy, carboxyl or Ester.R can be respectively C in each appearance₁-C₁₅Alkyl, C₃-C₆Naphthenic base, C_4-C₁₈Heterocycle, C_4-C₁₈Alkane heterocycle, C_6-C₁₈Virtue Base, C_7-C₂₅Alkaryl, C_7-25Aralkyl, C_5-C₁₈Heteroaryl or C_6-C₂₅Miscellaneous alkyl aryl or polyoxyalkylene.R can in each appearance To be respectively C_1-C₄Alkyl.R can be respectively methyl or ethyl in each appearance.On the ethylene replaced for 1,1- dicarbapentaborane Each ester group, R can be identical.Exemplary compounds be gluconic acid dimethyl malenate, diethylester, ethyl-methyl ester, Dipropyl, dibutyl, diphenyl and ethyl-ethyl ester；Or methylene dimethyl malenate and diethyl methylenemalonate (R is methyl or ethyl).

The vinyl compound that 1,1- dicarbapentaborane disclosed herein replaces shows sufficiently high purity, makes it possible to poly- It closes.The purity for the ethylene that 1,1- dicarbapentaborane replaces can be sufficiently high, so that 70 moles of % or more, preferably 80 in the course of the polymerization process Mole % or more, more preferable 90 moles of % or more, the % of even more preferably 95 moles of % or more, most preferably 99 moles or more The ethylene that more 1,1- dicarbapentaborane replaces is converted to polymer.Total weight based on the ethylene that 1,1- dicarbapentaborane replaces, 1,1- bis- The purity for the ethylene that carbonyl replaces is about 96 moles of % or bigger, about 97 moles of % or bigger, about 98 moles of % or bigger, about 99 Mole % or bigger or about 99.5 moles of % or bigger.The ethylene that 1,1- dicarbapentaborane replaces contains 4 moles of % or less 1, Bis- (the methylol)-methane of 1- dicarbapentaborane substitution -1,1-, 3 moles of % or less bis- (the hydroxyl first of 1,1- dicarbapentaborane substitution -1,1- Base)-methane, 2 moles of % or bis- (the methylol)-methane of less 1,1- dicarbapentaborane substitution -1,1-, 1 mole of % or less 1, Bis- (the methylol)-methane of 1- dicarbapentaborane substitution -1,1- or 0.5 mole of % or less 1,1- dicarbapentaborane substitution -1,1- methylol - Methane.Total weight based on the ethylene that 1,1- dicarbapentaborane replaces, the concentration of any impurity containing dioxanes group are preferably About 2 moles of % or smaller, more preferably about 1 mole of % or smaller are even more preferably about 0.2 mole of % or smaller, most Preferably about 0.05 mole of % or smaller.The integral molar quantity in ethylene replaced based on 1,1- dicarbapentaborane, olefin group is by class As hydroxyalkyl replace the total concentration of any impurity of (for example, passing through the Michael addition of alkene and water) to be preferably about 3 and rub You are % or smaller, more preferably about 1 mole of % or smaller, is even more preferably about 0.1 mole of % or smaller, most preferably It is about 0.01 mole of % or smaller.The ethylene that preferred 1,1- dicarbapentaborane replaces is by including distillation reaction product or intermediate reaction Product (for example, reaction product or intermediate reaction product of formaldehyde and malonate source) one or more (for example, two or More) preparation of the method for step.

Functional compound may include one or more methylene malonates that can be identical or different.

Catalyst

It is usually carried out in the presence of one or more catalysts according to the ester exchange reaction instructed herein.Transesterification catalysis Agent can be the ester or enzyme of acid, such acid.Ester exchange catalyst can be enzyme.Ester exchange catalyst can be lipase.It utilizes The ester exchange method of enzyme is disclosed in US 2014/0329980, and the document, which is incorporated by reference, to be incorporated herein for owning Purpose.

Ester exchange catalyst can be the ester of one or more acid or the acid, and the acid has in polar non-solute There is the pKa of about -5 to about 14.Acid or acid esters can be with the transesterifications of every molar equivalent containing about 3.0 molar equivalent of ester compounds or more The amount of few acid or acid esters exists.When catalyst is acid or when acid esters, this method can about 20 DEG C to about 160 DEG C at a temperature of It carries out.Ester exchange catalyst can be lipase-catalyzed dose.When catalyst is lipase-catalyzed dose, step of transesterification is about 20 DEG C to carrying out at a high temperature of 70 DEG C.During ester exchange reaction, volatile byproducts can be formed and removed from reaction mixture. Volatile byproducts can be removed from reaction mixture by applying vacuum.Volatile byproducts can be alcohol.

Catalyst can be acid or its ester.It is disclosed in what on July 31st, 2015 submitted using the ester exchange method of acid or ester In U.S. Patent Application Serial Number 14/814,961, which, which is incorporated by reference, is incorporated herein for all mesh 's.Any acid or its ester that catalyzed transesterification can be used simultaneously to minimize side reaction.In some embodiments, described Acid or the acid for being used to form ester are the acid with the pKa in polar non-solute such as acetonitrile or dioxanes, as disclosed below. In particular, being selected pKa with effectively catalyzed transesterification, while making catalyst in side reaction and reaction mixture Concentration minimizes.Acid used can have about -5 or bigger, about -3 or bigger or about 1.0 or bigger pKa.Acid used can With about 14 or smaller, about 11 or smaller or about 9 or smaller pKa.Acid can be the cloth with pKa disclosed in this invention Lanace platform moral acid.Catalyst can be super acid or its ester.Super acid refers to that acid strength is greater than the acid of the intensity of 100% sulfuric acid.In acid In the context of catalyst, ester refers to the compound that the hydrogen on wherein acid is replaced by alkyl, optimizing alkyl.Super acid is that intensity is big In 100% sulfuric acid intensity and pKa less than 100% sulfuric acid and less than 8, more preferably less than about 5, most preferably less than about 2 acid. " the Equilibrium Acidities of Super that the measurement of acid strength is announced based on Kutt et al. on December 17th, 2010 Acids, " Journal of Organic Chemistry, volume 76 page 391 to 395,2011, the document was with the side of reference Formula is incorporated herein.Exemplary super acid includes trifluoromethayl sulfonic acid (trifluoromethanesulfonic acid), sulphation tin oxide, trifluoromethanesulfonic acid oxygen Change tin, sulfated zirconia, trifluoromethanesulfonic acid zirconium oxide and trifluoromethanesulfonic acid HZSM-5.Most preferred super acid is fluoroform Sulfonic acid and fluosulfonic acid.

Exemplary acids catalyst includes trifluoromethanesulfonic acid, fluosulfonic acid and sulfuric acid.For needing mono-substituted reaction (on alcohol Only one hydroxyl is replaced by transesterification), it may be necessary to pKa value is equal to or higher than the weaker acid of sulfuric acid.The example of such acid includes Sulfuric acid or methanesulfonic acid.For needing disubstituted reaction (two hydroxyls on alcohol are replaced by transesterification), it may be necessary to pKa value etc. In or lower than sulfuric acid stronger acids.The example of such acid includes sulfuric acid, fluosulfonic acid and trifluoromethanesulfonic acid.It is polysubstituted for needing It reacts (more than two hydroxyl on alcohol), the selection of acid catalyst can be similar to two substitution reactions, but the reaction time may need to increase Add.The acid esters that can be used as catalyst includes trifluoromethanesulfonic acid Arrcostab.

Catalyst can be mixed with reactant, can also be supported on matrix such as film or inert carrier such as porous support structure (catalyst can be heterogeneous).The catalyst not being supported is commonly referred to as homogeneous catalyst.Catalyst can be catalyzed ester friendship Any concentration for changing reaction uses.The amount of catalyst for reaction depends on the type of selected catalyst.The concentration of catalyst For about 3 molar equivalents or smaller in the ester compounds of the experience transesterification of every equivalent；About 1 molar equivalent or smaller；About 0.5 mole Equivalent is smaller；About 0.1 molar equivalent or smaller.The concentration of catalyst be every equivalent experience transesterification ester compounds in about 0.01 molar equivalent is bigger；Most preferably about 0.1 molar equivalent is bigger.It can be used the concentration compared with cited higher Catalyst.Such as the WO 2013/ of the US 8,609,885 and 8,884,051 of Malofsky et al. and Malofsky et al. Disclosed in 059473, about the use of compound, in 1, the 1- disubstituted olefin compound of recycling sour presence there may be Problem, and need the acid in product to be used with low concentration.If containing the acid of high-content in final product, it may be necessary to Additional purifying or removal step.The amount realizes effectively between catalysis and the demand to low acid concentration in the product for using Balance.It is less than in the embodiment of those of sulfuric acid acid in catalyst selected from sulfuric acid or pKa value, it is such in reaction mixture to urge The concentration of agent is preferably in the upper limit of range described herein.

Catalyst may include enzyme catalyst or be made of completely enzyme catalyst.It can be used any suitable for catalytic transesterification The enzyme catalyst of reaction.In 7,972,822 B2 of United States Patent (USP), (Gross et al. was sent out various enzyme catalysts on July 5th, 2011 Cloth, see, for example, the 8th column 2-4 and 7-35 row), United States Patent (USP) 5,416,927 A (Zaks et al., on May 31st, 1994 send out Cloth, see, for example, the 64th row of the 2nd column to the 12nd row of the 3rd column), United States Patent (USP) 5,288,619 A (Brown et al., in 1994 years 2 Months 22 days issue, see, for example, the 18th row of the 4th column to the 17th row of the 5th column), U.S. Patent Application Publication 2016/177,349 A1 (Addy et al. is announced on June 23rd, 2016, see, for example, paragraph 0046-0048), U.S. Patent Application Publication 2014/ (Nielsen et al. was announced, see, for example, being described in paragraph 0026-0029) 0017741 A1 on January 16th, 2014； Disclosure is herein incorporated by reference.

Many different enzymes can be used for the enzymatic catalysis ester exchange reaction of wax ester, and the wax ester is biological including being originated from/being obtained from Those of organism those of those of is synthetically prepared and is manually prepared completely with biology and/or synthesis mode.For making For those of lipase enzyme, these enzymes may include one of lipase from following organism, some, any or any group It closes: aspergillus niger (Aspergillus niger), aspergillus oryzae (Aspergillus oryzae), bacillus subtilis (Bacillus Subtilis), Bacillus thermocatenulatus, Burkholderia cepacia (Burkholderia cepacia), Pod shell burkholderia (Burkholderia glumae), candida rugosa (Candida rugosa), South Pole vacation silk ferment Female A (Candida antarctica A), antarctic candida B (Candida antarctica B), Candida cylindracea (Candida cylindracea), Candida parapsilosis (Candida parapsilosis), dyeing slime bacteria (Chromobacterium viscosum), geotrichum candidum (Geotrichum candidum), Geotrichum kind (Geotrichum Sp.), conspicuous Mucor of rice (Mucor miehei), thin cotton like humicola lanuginosa (Humicola lanuginose), penicillium camembertii (Penicillium camembertii), penicillium chrysogenum (Penicillium chrysogenum), penicillium roqueforti (Penicillium roquefortii), Pseudomonas cepacia (Pseudomonas cepacia), pseudomonas aeruginosa (Pseudomonas aeruginosa), Pseudomonas fluorescens (Pseudomonas fluorenscens), Pseudomonas fragi (Pseudomonas fragi), Pseudomonas alcaligenes (Pseudomonas alcaligenes), pseudomonas mendocina (Pseudomonas mendocina), unrooted rhizopus (Rhizopus arrhizus), rhizomucor miehei (Rhizomucor Miehe), Staphylococcus hyicus (Staphylococcus hyicus), staphylococcus aureus (Staphylococcus Aereus), staphylococcus epidermis (Staphylococcus epidermidis), walsh staphylococcus (Staphylococcus Warneria), staphylococcus xylosus (Staphylococcus xylosus), the thin thermophilic hyphomycete (Thermomyces of cotton like Lanuginosus), aspergillus kind (Aspergillus sp.), bacillus kind (Bacillus sp.), Burkholder Bordetella kind (Burkholderia sp.), candida kind (Candida sp.), Chromobacterium (Chromobacterium Sp.), Geotrichum kind (Geotrichum sp), mucor kind (Mucor sp), Humicola kind (Humicola sp), blueness Mould belong to kind of (a Penicillium sp), pseudomonas kind (Pseudomonas sp), rhizopus kind (Rhizopus sp.), Staphylococcus kind (Staphylococcus sp) and thermophilic fungal belong to kind of (a Thermomyces sp.).Lipase may include with A kind of lower or any combination is substantially made of a kind of following or any combination: Lai free Novozymes A/S of Bagsvaerd, Denmark are sold and are fixed on trade name LIPOZYME TL IM or LIPEX and equally prepared by Novozymes Matrix on the thermophilic hyphomycete of thin cotton like lipase；By Novozymes, A/S is originated from south with what trade name NOVOZYM was sold The lipase of pole Candida；By Novozymes with trade name CALB L, 435 NOVOZYME, NOVOCOR AD L and Those of LIPOLASE 100L sale；By c-LEcta, GMBH of Leipzig, Germany with trade name CALB, CALA and Those of CRL sale；By Amano Enzyme Inc.of Nagoya, Japan with trade name LIPASE A " AMANO " 12, LIPASE AY“AMANO”30SD、LIPASE G“AMANO”50、LIPASE R“AMANO”、LIPASE DF“AMANO”15、 Those of LIPASE MER " AMANO " and NEWLASE F sale；By Meito Sangyo Co., Ltd., of Nagoya, Japan is with trade name LIPASE MY, LIPASE OF, LIPASE PL, LIPASE PLC/PLG, LIPASE QLM, LIPASE QLC/QLG, LIPASE SL and LIPASE TL those of are sold, i.e., lipase from antarctic candida A, false from the South Pole The lipase of silk yeast B and lipase from candida rugosa.In various embodiments, lipase preferably and herein Any lipase in patent application disclosed and disclosed herein has at least 60%, at least 70%, at least 80%, extremely Few 90%, at least 95%, at least 96%, at least 97%, at least 98% or even at least 99% identity, all patent applications Previously it has been incorporated by reference.

Polymerizable system

It is related to polymerizable system according to the one aspect instructed herein comprising functionalized polymeric and one or more Asias Methylmalonic acid ester monomer.Methylene malonate monomer can be selected, so that it is by the alkenyl with functionalized polymeric Copolymerization.It should be appreciated that the copolymerization of functionalized polymeric and one or more methylene malonate monomers can obtain including first The block copolymer of polymer blocks and second polymer block, the first polymer block include methylene malonate list Body, substantially by methylene malonate monomer composition or completely by methylene malonate monomer composition, second polymerization Object block includes centre polymer part (for example, polymer containing polyalcohol), be substantially made of centre polymer part or Person is made of centre polymer part completely.If functionalized polymeric include two or more alkenyls spaced apart (for example, Methylene malonate compound spaced apart, preferably on the different ends of centre polymer part), then the functionalization polymerize Object can provide the crosslinking of methylene malonate monomer.

In the functional compound with alkenyl of functionalized polymeric, any methylene malonate as described herein Compound can be used for the monomer in polymerisable compound.It should be appreciated that methylene malonate monomer can be used partly or entirely Dimer, tripolymer or longer oligomer (for example, with about 4 to 50, about 4 to 15 or about 4 to 8 degree of polymerization) replace.

Second polymer block (e.g., including the block of the polymer containing polyalcohol) it can be than first polymer block more It is flexible, and flexibility and/or impact resistance are provided for block copolymer.

Polymerizable system may include enough stabilizers to prevent or minimize the polymerization of polymerizable system.This method can wrap Include activation polymerizable system with polymeric methylene malonate monomer and be connected to centre polymer part alkenyl the step of.

Based on the total weight of first polymer block, one of first polymer block or a variety of methylene malonates The amount of monomer is preferably about 20 weight % or more, more preferably about 50 weight % or more, is even more preferably about 75 weight % or more, most preferably about 85 weight % or more.Based on the total weight of first polymer block, the first polymerization The amount of one of object block or a variety of methylene malonate monomers can be about 100 weight % or less, about 99 weight % or Less, about 97 weight % or less, about 93 weight % or less, or about 88 weight % or less.It is embedding based on second polymer The amount of the total weight of section, the polyalcohol in second polymer block is preferably about 25 weight % or more, more preferably about 60 weight % or more are even more preferably about 80 weight % or more, most preferably about 90 weight % or more.It is based on The total weight of second polymer block, the amount of the polyalcohol in second polymer block can be about 100 weight % or less, about 98 Weight % or less, about 96 weight % or less or about 94 weight % or less.One or more methylene malonate lists The weight of body and the weight ratio of functionalized polymeric can be about 0.05 or bigger, about 0.10 or bigger, about 0.20 or bigger, about 0.45 or bigger or about 0.60 or bigger.The weight of one or more methylene malonate monomers and functionalized polymeric Weight ratio can be about 0.99 or smaller, about 0.96 or smaller, about 0.92 or smaller, about 0.88 or smaller, about 0.84 or smaller Or about 0.80 or smaller.

Functionalized polymeric and/or polymerizable system can be used for film or coating.The thickness of film or coating can be about 0.001 μm Or bigger, about 0.1 μm or bigger, about 1 μm or bigger or about 2 μm or bigger.The thickness of coating or film be preferably from about 200 μm or It is smaller, more preferably about 50 μm or smaller, most preferably about 20 μm or smaller.

It can be used in cross-linked polymer according to the functionalized polymeric and/or polymerizable system instructed herein.Cross-linked polymeric Object may include 1, the 1- disubstituted olefin monomer (for example, methylene malonate monomer), basic of functionalized polymeric and polymerization On be made of them or be made of completely them.Total weight based on cross-linked polymer, the functionalized poly in cross-linked polymer The total amount for closing the 1,1- disubstituted olefin monomer of object and polymerization can be about 5 weight % or more, about 20 weight % or more, about 45 Weight % or more, about 70 weight % or more or about 90 weight % or more.Total weight based on cross-linked polymer, crosslinking The total amount of the 1,1- disubstituted olefin monomer of functionalized polymeric and polymerization in polymer can be about 100 weight % or less or About 98 weight % of person or less.

Method

Functionalized polymeric can by make include polyalcohol and with 1,2,3 or more hydroxyl polymer with One or more functional compounds including alkenyl react to prepare.Functional compound may include being carried out instead by ester exchange reaction The ester group answered:

Catalyst can be used to accelerate ester exchange reaction in this method.For making the polymer based on polyalcohol and including ester The preferred catalyst of functional compound reaction includes enzyme catalyst or acid catalyst.

This method can be batch methods, continuation method or their combination.For example, continuation method may include by a kind of or A variety of reactants (for example, compound of 1,1- disubstituted compound and formation central part) are fed in flow reactor Step.Can be by catalyst charge into reactor, or catalyst can be provided to reactor.For example, at least one of reactor Point may include have the filler of catalyst or catalyst may be present on the surface of reactor (for example, the surface of reactor or The surface of component in reactor).Flow reactor can be tubular reactor or be suitable for being inserted at one end at least one anti- It answers object and removes other reactors of at least one reaction product in opposite end.Preferably, flow reactor is tubular reactor, It includes the catalyst of filling in the reactor.The temperature of continuation method is preferably about 10 DEG C or higher, more preferably about 15 DEG C or higher, most preferably about 20 DEG C or higher.Reaction temperature is preferably about 150 DEG C or lower.When using acid catalysis When agent, reaction temperature is preferably about 40 DEG C to about 150 DEG C, more preferably about 60 DEG C to about 150 DEG C.When using enzyme catalyst When, reaction temperature is preferably about 80 DEG C or lower, more preferably about 70 DEG C or lower, most preferably about 60 DEG C or more It is low.

It include one or more methylene malonate monomers and one or more functionalized polymeric (examples for polymerizeing Such as, including polyalcohol) composition can be used in the method for forming block copolymer and be suitable for polymeric methylene malonate list Any polymerization of body.Functional group on functionalized polyol preferably includes the alkenyl suitable for anion polymerisable.Preferably, Functional group includes the methylene malonate identical or different with methylene malonate monomer.It is highly preferred that functional group includes Methylene malonate also serves as the monomer in the polymerization to form block copolymer.

Ester exchange method can be used for making each of hydroxyl of polyhydric alcohol polymer (for example, each in terminal hydroxyl It is a) it is reacted with 1,1- disubstituted olefin compound, form functionalized polymeric.If 1,1- disubstituted olefin with it is two different Polyhydric alcohol polymer reaction, then can extend the length of polyhydric alcohol polymer and the centre polymer part in functionalized polymeric Middle addition alkenyl.This chain extension reaction is avoided to may be advantageous.By selecting 1,1- disubstituted olefin compound, by making With excessive 1,1- disubstituted olefin compound, or both, it is possible to reduce, substantially eliminate or completely eliminate functionalized polymeric Chain extension reaction in forming process.For example, 1,1- disubstituted olefin compound may include with the list for being able to carry out transesterification The compound of ester group is substantially made of the compound.For another example, 1,1- disubstituted olefin compound may include two or more Multiple ester groups and with excessive concentration presence so that there are unreacted 1,1- disubstituted olefin chemical combination after ester exchange reaction Object.The amount of excessive 1,1- disubstituted olefin compound may depend on the molecular weight of polyhydric alcohol polymer, polyhydric alcohol polymer Hydroxyl in compatibility and polyhydric alcohol polymer between mobility, polyhydric alcohol polymer and 1,1- disubstituted olefin compound The number of (for example, terminal hydroxyl).Preferably, there are excessive 1,1- disubstituted olefin compounds (that is, it is anti-to can be used for transesterification The terminal hydroxyl number for the polyhydric alcohol polymer answered should be less than the 1,1- disubstituted olefin compound that can be used for ester exchange reaction Molecule amount).Preferably, the molar ratio of the weight of 1,1- disubstituted olefin compound and polyhydric alcohol polymer is about 1.5 or more Greatly, even more preferably it is about 1.9 or bigger, is even more preferably about 2.3 or bigger, is even more preferably about 3 or more It greatly, is even more preferably about 4 or bigger, most preferably about 4 or bigger.When the molecular weight of polyhydric alcohol polymer is relatively high (for example, the molecular weight of polyhydric alcohol polymer and 1, the ratio between the molecular weight of 1- disubstituted olefin compound is about 6 or more greatly or about 15 or bigger) when, excessive 1,1- disubstituted olefin compound can be used to reduce the viscosity of mixture and/or accelerate sealing end anti- It answers.Therefore, the molar ratio of 1,1- disubstituted olefin compound and polyhydric alcohol polymer can be much larger than 4 (for example, about 10 or more Greatly, about 30 or bigger or about 100 or bigger).

This method may include that some or all of unreacted 1,1- disubstituted olefin compound is polynary with sealing end The step of alcohol separates.It is also expected to minimizing the amount of unreacted 1,1- disubstituted olefin compound.For those reasons, it is expected that The weight ratio of 1,1- disubstituted olefin compound is usually lower (for example, reducing excessive 1,1- disubstituted olefin compound And/or it can be readily removable by separation or other technologies.The weight and polyhydric alcohol polymer of 1,1- disubstituted olefin compound Weight ratio be preferably about 40 or smaller, more preferably about 20 or smaller, be even more preferably about 10 or smaller, most Preferably about 5 or smaller.However, the weight ratio higher than 40 can be used.It should be appreciated that some unreacted 1,1- bis- replace alkene Hydrocarbon compound can be used in polymerisable compound, so as to 1,1- disubstituted olefin compound and be connected on polyhydric alcohol polymer Alkenyl copolymerization.Ester exchange reaction can substantially avoid or avoid completely 1,1- disubstituted olefin compound and multiple hydroxyls anti- It answers.

Test method

Any numerical value as described herein includes all values for being increment from lower value to high value using a unit, premise item Part is that there are the intervals of at least two unit between any lower value and any high value.For example, if set forth the amount of component Or the value of process variable such as temperature, pressure, time etc. is, for example, 1 to 90, it is therefore preferable to 20 to 80, more preferably 30 to 70, It is intended to clearly enumerate 15 to 85,22 to 68,43 to 51,30 to 32 etc. value in the present specification.For the value less than one, One unit is considered as 0.0001,0.001,0.01 or 0.1, is depended on the circumstances.These are only specifically intended examples, and institute The all possible combinations for the numerical value between minimum and peak enumerated should be considered clear in a similar manner in this application Statement.As can be seen that the introduction for being expressed as the amount of " parts by weight " herein also contemplates phase homotype as expressed in weight percent It encloses.Therefore, it is also set in specific embodiment with the expression in the range of " ' gained of x ' parts by weight polymerize blend compositions " indicates The introduction of the range of identical " x " amount in terms of the weight percent that gained polymerize blend composition is want.

Unless otherwise stated, all ranges all include all numbers between endpoint and endpoint.Incorporation range uses "about" or "approximately" be suitable for range both ends.Therefore, " about 20 to 30 " are intended to cover " about 20 to about 30 ", including refer at least to Fixed endpoint.

The disclosure of all articles and bibliography, including patent application and publication, be incorporated by reference with For all purposes.It should include identified element, ingredient, component for describing combined term " substantially by ... form " Or step, and will not substantially influence other elements, ingredient, component or the step of the basic and novel characteristics of combination.It uses Term "comprising" or " comprising " also contemplate substantially to describe the combination of element herein, ingredient, component or step by member The embodiment that element, ingredient, component or step form.

Multiple element, ingredient, component or step can be provided by single integrated component, ingredient, component or step.Or Person, single integrated component, ingredient, component or step can be divided into individual multiple elements, ingredient, component or step.Description Element, ingredient, component or step "a" or "an" disclosure be not intended to exclude other elements, ingredient, component or Step.

It should be appreciated that above description be intended to it is illustrative and not restrictive.After reading above description, in addition to providing Example except, many embodiments and it is many application will be apparent for a person skilled in the art.Cause This, the scope of the present invention should not be determined with reference to above description, but should refer to appended claims and these claims The full scope of the equivalent assigned determines.The disclosure of all articles and bibliography, including patent application and go out Version object, is incorporated by reference with for all purposes.Any aspect of presently disclosed subject matter is in following following claims In omission be not disclaimer to such theme, be also not construed as inventor and be not considered as that such theme is disclosed sheet A part of subject matter.

Embodiment

Examples 1 and 2

Embodiment 1 is the reaction mixture for including straight chain aromatic polyester polyols, and the straight chain aromatic polyester polyols exist Two ends methylene malonate monomer and residual monomer sealing end.Embodiment 2 is the remaining methylene malonate of removal The filtrate of embodiment 1 after monomer.

About 6g aromatic polyester polyols and about 30g diethyl methylenemalonate monomer are mixed in round-bottomed flask, until Polyalcohol is dissolved or is otherwise dispersed in monomer.Aromatic polyester can be commercially available from INVISTA 5100 polyalcohol of HT, per molecule averagely have about 2.2 hydroxyls, and hydroxyl value is about 295mgKOH/g, and the viscosity at 25 DEG C is About 6,000cps.Aromatic polyester polyols include the repetition with aromatic group (for example, bisphenol residue) and ester group along main chain Unit.

About 3g enzyme catalyst (the diethyl methylenemalonate monomer of about 10% weight) is added in reaction mixture. Enzyme catalyst is 435 immobilized lipase of NOVOZYM that can be commercially available from NOVOZYMES (Denmark).By round-bottomed flask It is connected on the rotary evaporator for the temperature for being maintained at about 45 DEG C, and with 100rpm rotation 2 hours under the vacuum of 200mm Hg. At the end of reaction, a small amount of aliquot is taken to carry out NMR analysis, and filter remaining mix using the tampon in 100ml syringe Object is closed to go to dezymotize.Filtrate (that is, reaction mixture) be about 70 weight % diethyl methylenemalonate monomers (that is, DEMM) and The blend of the aromatic polyester polymer of about 30 weight % sealing end.Figure 1A be include DEMM reaction mixture proton H NMR spectroscopy Figure.As shown in Figure 1B, the formation with the novel substance of methylene double bond is confirmed in the region 6.535-6.583ppm of spectrogram, and And remaining DEMM is confirmed in the region 6.51-6.535ppm of spectrogram.

The aromatic polyester of sealing end can have one or more features as shown below:

It is prepared and is taken on cold-rolled steel sheet using the reaction mixture for the aromatic polyester polymer for including remnants DEMM and sealing end Shearing sample is connect, uses sodium benzoate in 0.1 weight % ethyl alcohol as activator.It is solid that room temperature is measured at least three sample Lap shear strength after changing 24 hours.Average lap shear strength is about 5.7MPa.By other lap shear sample in room Temperature descends solidification 24 hours, then aging 2 days in 120 DEG C of baking oven.After aging, lap shear strength increases above 10MPa.According to Letter, the increase of lap shear strength be because of heat cross-linking caused by result.The armaticity of polyalcohol leads to the large size with high rigidity The adhesive composition of backbone structure.

By including unreacted DEMM reaction mixture sample in aluminium dish using a large amount of tetramethylguanidine (that is, TMG) into Row solidification.Resulting polymers do not dissolve in methylene chloride (that is, DCM).This shows high-crosslinking-degree.

Embodiment 2

Hexane is added in the reaction mixture sample of the embodiment 1 including unreacted DEMM.Hexane is remaining The good solvent of DEMM is the poor solvent of polyalcohol and capped polyols.It will be in capped polyols and reaction mixture Excessive DEMM separation.Then capped polyols are dried in vacuo to remove any remaining hexane.Then, by using with react The lap shear of mixture tests identical curing time preparation lap shear sample to test the sealing end aromatic polyester of separation Adhesion property.After solidifying 24 hours at room temperature, the lap shear strength of isolated end capped polyesters is about 4MPa, at 120 DEG C It is 6.6MPa after solidification 2 days.It is believed that the bulky structure of centre polymer part and the alkenyl of low concentration make isolated sealing end more The anionic polymerisation of first alcohol becomes difficult.Compared with Example 2, can be increased using methylene malonate monomer such as DEMM viscous Attached property, as shown in the relatively high-adhesiveness of embodiment 1.

Embodiment 3

Embodiment 3 is the reaction mixture for including the pure and mild remaining methylene malonate monomer of blocked aliphatic polyester polyols.

By making TERRIN^TM168 polyalcohols are reacted with DEMM prepares embodiment to block polyalcohol.TERRIN^TM 168 aliphatic polyester polylols can be commercially available from INVISTA, and by glycol (including diethylene glycol (DEG), HO-C₂H₄-O-C₂H₄-OH) It is prepared with carboxylic acid functional monomers (mainly adipic acid and 6 hydroxycaproic acid).

By about 30g DEMM and about 6g TERRIN^TM168 (about 5:1 weight ratios) mix in round-bottomed flask, until polynary Alcohol is dissolved or dispersed in DEMM monomer.About 3g is added into flask435 enzyme catalysts (about 10 weight % DEMM).Flask is connected on the rotary evaporator for being maintained at 45 DEG C, and is rotated under the vacuum of 200mm Hg with 100rpm 2 hours.At the end of reaction, a small amount of aliquot is taken to carry out NMR analysis, and filter and remain using the tampon in 100ml syringe Remaining mixture is to go to dezymotize.Reaction mixture (that is, filtrate) be include unreacted DEMM and envelope that weight ratio is about 75:25 The blend of the comprised of aliphatic polyester polymers at end.

Reaction mixture sample is solidified in aluminium dish using a large amount of tetramethylguanidine (TMG).Resulting polymers are insoluble In DCM, show high-crosslinking-degree.After being washed with DCM, tested using thermogravimetry (TGA) with the rate of heat addition of about 10 DEG C/min Polymer.TGA scanning is as shown in Figure 2.Cause the decomposition of weight loss since about 250 DEG C of temperature.50% weight loss Occur at greater than about 300 DEG C of temperature (for example, about 335-365 DEG C).In contrast, corresponding to 50 weights of DEMM homopolymer The temperature of amount % weight loss (such as being measured by TGA) is typically about 210 DEG C, and corresponds to crosslinking DEMM (by DEMM 0 weight %DEMM of polymerase 17 in the presence of carrying out transesterification and the about 30 weight % crosslinking agents that prepare with hexylene glycol and prepare) 50 The temperature of weight % weight loss is greater than about 300 DEG C.It is believed that these TGA are the result shows that blocked aliphatic polyester polyol and DEMM are total It polymerize and causes the crosslinking of DEMM.

Embodiment 4 and embodiment 5

Embodiment 4 is the reaction mixture for including polycarbonate polyol, polycarbonate polyol methylene third Two acid ester monomers and residual monomer sealing end.Embodiment 5 is the end-capping polycarbonate polyalcohol removed after residual monomer.

By mixing about 30g DEMM and about 6g PACAPOL in round-bottomed flask^TMF250 polycarbonate polyol (about 5: 1 weight ratio), until polyalcohol is dissolved or dispersed in DEMM monomer, to prepare embodiment 4.PACAOPOL^TMF250 is can The aliphatic polycarbonate polyalcohol commercially available from INSTRUMENTAL POLYMER TECHNOLOGIES.PACAPOL^TM F260 Slightly branching has 100% solid content, and has hydroxy functional group, and equivalent weight is about 225g/eq.In order to promote poly- carbonic acid Solvent (for example, toluene) can be used in the mixing of ester polyol and methylene malonate monomer.By about 3g CLEA 102B4 Antarctic candida isotype B/ powder, cross-linked enzyme aggregate (about 10 weight %DEMM) are added to flask as catalysts In.CLEA 102B4 can be commercially available from CLEA TECHNOLOGIES B.V. (Delft, The Netherlands).By flask It is connected on rotary evaporator, it is small that reaction carries out 2 at 45 DEG C, under the vacuum of about 200mm Hg with the revolving speed of about 100rpm When.At the end of reaction, a small amount of aliquot is taken to carry out NMR analysis, and remaining using the tampon filtering in 100ml syringe Substance is to go to dezymotize.Reaction mixture (filtrate) includes the DEMM and end-capping polycarbonate polyalcohol that weight ratio is about 75:25 Blend.

End-capping polycarbonate polyalcohol can have following structure shown in one or more features:

Reaction mixture is solidified in aluminium dish using TMG.Resulting polymers do not dissolve in DCM, show high-crosslinking-degree.

Embodiment 5 is prepared by removing unreacted methylene malonate monomer from embodiment 4.By to implementation Hexane is added in the reaction mixture of example 4 to prepare embodiment 5.Hexane is that polycarbonate polyol and end-capping polycarbonate are polynary The poor solvent of alcohol.After removing DEMM, capped polyols are dried in vacuo at room temperature to remove any remaining hexane.

Isolated end-capping polycarbonate polyalcohol is solidified in aluminium dish using TMG.Resulting polymers do not dissolve in DCM shows high-crosslinking-degree.

Fig. 3 is the proton NMR spectra of isolated end-capping polycarbonate polyalcohol.

The coating of the reaction mixture (including end-capping polycarbonate polyalcohol and unreacted DEMM) of embodiment 4 is coated On processed cold-rolled steel sheet.By the BUTYL CELLOSOLVE of 0.1% sodium benzoate of cold-rolled steel sheet^TMSolvent is (from DOW CHEMICAL COMPANY is commercially available) processing, to cause the polymerization of DEMM.Reaction mixture is coated simultaneously using Meyer stick 10 Solidify at room temperature about 24 hours.Gained coating with a thickness of about 25 μm.According to ASTM D522-93, when steel plate is curved in mandrel When about 180 ° bent, coating keeps adhesiveness, shows that coating has high suppleness.In processed cold-rolled steel sheet (that is, DEMM homopolymerization Object) on only with DEMM monomer prepare sample similar crooked test cause coating bending when from surface of steel plate peeling.Therefore, Addition end-capping polycarbonate improves the flexibility of the product of polymerization DEMM.

Embodiment 6

Embodiment 6 is the reaction mixing for including the polybutadiene polyol blocked with methylene malonate monomer and monomer Object.

The example of polybutadiene polyol is as follows:

By mixing about 40g DEMM and about 10g POLY in round-bottomed flaskR-20LM hydroxy-end capped polybutadiene Olefine resin (that is, HTPB) (that is, weight ratio is about 4:1), until polyalcohol is dissolved or dispersed in DEMM monomer, to prepare reality Apply example 6.Resin can be commercially available from CRAY VALLEY HYDROCARBON SPECIALTY CHEMICALS, Its number-average molecular weight is about 1200, and glass transition temperature is about -70 DEG C, and each chain averagely has about 2.5 hydroxyls. About 20% monomeric unit is 1,2 additions in HTPB, and about 80% is 1-4 addition.Then about 4g CLEA is added into flask 102B4 enzyme catalyst (DEMM of about 10 weight %).Flask is connected on the rotary evaporator for being maintained at about 45 DEG C, and about With about 100rpm rotation 2 hours under the vacuum of 200mm Hg.At the end of reaction, a small amount of aliquot is taken to carry out NMR analysis.Make Remaining substance is filtered with the tampon in 100ml syringe to go to dezymotize.Reaction mixture (that is, filtrate) be include that weight ratio is The blend of the polybutadiene of the unreacted DEMM and sealing end of about 75:25.

Terminated polybutadiene can have following structure shown in one or more features:

Fig. 4 shows the H-NMR of reaction mixture.Methene proton in HTPB by OH group is usually on H-NMR spectrum It is shown as 4.1 and 4.3ppm.After ester exchange reaction, substantially reduced in the reactive mixture (for example, disappearing or seeming non- It is often faint).

These results have realized the sealing end of polybutadiene.

Embodiment 7

Embodiment 7 is the reaction mixture for including terminated polybutadiene and unreacted methylene malonate monomer.

Embodiment 7 is prepared in continuous tower-type reactor, and temperature is about 30 DEG C, and pressure is about 150mmHg, and feed flow rate is The weight ratio of about 100mL/h, DEMM and HTPB are about 5:1.Stainless steel feed containers package high temperature adhesive plaster is placed in agitating plate On to keep the mixture of DEMM and HTPB to homogenize.It will open into the feeding line package high temperature adhesive plaster of reactor bottom and carry out Heat-insulated processing.Reactor is loaded into collet and is heated with oil heater, and is thermally insulated to reduce heat loss.Temperature is visited Head is placed in reactor, feeding line and feed containers to be kept for 30 DEG C.DEMM/ is pumped with about 100mL/h using peristaltic pump HTPB mixture.Mixture is fed in reactor from bottom, is contacted with CLEA 102B4 enzyme, and is pumped from reactor head Out.It is packed into about 25g CLEA 102B4 enzyme in the reactor.Vacuum is extracted out from reactor head, and product is taken out above outlet. Product (that is, reaction mixture) is pumped into collection vessel using peristaltic pump, and per hour via H- after starting collection product NMR analysis.As above for described in embodiment 6, transesterification is confirmed by H-NMR.

Embodiment 8:

Embodiment 8 be include the methanol sealing end dimethyl silicone polymer and unreacted blocked with methylene malonate monomer Methylene malonate monomer reaction mixture.

Poly- (diformazan is blocked by mixing about 60g DEMM and about 12g GELEST DMS C-21 methanol in round-bottomed flask Radical siloxane) (5:1 weight ratio) until polyalcohol is dissolved or dispersed in DEMM monomer prepare embodiment 8.GELEST DMS C-21 can be from GELEST, and INC (Morrisville, PA) is commercially available, and number-average molecular weight is about 4,500 to 5,000, specific gravity It is about 0.98, viscosity is about 110-140cSt.CAS number are as follows: 156327-07-0.About 6g CLEA 102B4 is added into flask Enzyme catalyst (DEMM of 10 weight %).Flask is connected on the rotary evaporator for being maintained at 45 DEG C, and 200mm Hg's With 100rpm rotation 2 hours under vacuum.At the end of reaction, using the tampon filtering mixture in 100ml syringe to remove Enzyme.Gained reaction mixture (that is, filtrate) is the blend of the DEMM that weight ratio is about 75-25 and endcapped siloxanes polyalcohol.

Endcapped siloxanes polyalcohol can have following structure shown in one of feature or any combination:

Using Meyer stick 10 reaction mixture of the siloxanes of sealing end and unreacted DEMM are coated in and to be caused in advance On (0.1% sodium benzoate in butyl cellosolve) cold-rolled steel sheet, and solidify at room temperature 24 hours, then adds at 82 DEG C Heat 1 hour.Coating with a thickness of 25 μm.According to ASTM D522-93, after about 180 ° are bent in mandrel, coating is kept and steel plate Adherency.This shows that coating has high suppleness.

Coating shows hydrophobic property.For example, contact angle of the water on coating is about 70 °.In contrast, coated in drawing in advance Water contact angle of the coating of only DEMM monomer on the cold-rolled steel sheet of hair on coating is about 55-55 ° (that is, low about 15-20 °). As described in Example 8, terminated polysiloxane polyalcohol can be used for be assigned and being dredged based on the coating of methylene malonate such as DEMM It is aqueous.

Embodiment 9

Embodiment 9 be include with methylene malonate monomer block polyalkylene glycol and unreacted methylene third The reaction mixture of two acid ester monomers.The sealing end of polyalkylene glycol is carried out using PEGylation processes.

By CARBOWAX^TM300 polyethylene glycol of PEG (can be commercially available from DOW CHEMICAL COMPANY) pass through by Alumina column purifying, obtains remaining base catalyst.The number-average molecular weight of polyethylene glycol is about 285 to 300g/ moles, and hydroxyl value is About 340 to 394mg KOH/g, and melting range is about -15 DEG C to about -8 DEG C, and melting heat is about 37cal/g.In 250mL circle About 30g (0.17mol) DEMM, about 3g (10 weight %DEMM) CLEA 102B4 enzyme and about 16.6g are packed into the flask of bottom (0.083mol) PEG 300 (passes through aluminium oxide).Flask is connected to the rotary evaporator with about 200mm Hg vacuum, and is added Heat continues 2 hours to about 45 DEG C.Ethyl alcohol is removed in vacuo as byproduct of reaction.Then using the tampon in 20ml syringe from anti- It answers and filters enzyme in mixture.NMR the result shows that, about 35% DEMM is reacted with PEG, about 65% DEMM be left reaction mixing Unreacted monomer in object.Fig. 5 shows the NMR of reaction mixture.

Terminated polymer may have a structure such that comprising the centre polymer part containing polyalkoxide and have The terminal methylene phenyl malonic ester group of one or more (or whole) features as shown below:

Using Meyer stick 10 by the reaction mixture of the PEG of sealing end and DEMM be coated in cause in advance (in butyl cellosolve In 0.1% sodium benzoate) on cold-rolled steel sheet, after 24 hours are fully cured at room temperature, obtain 25 microns of thick coatings, then It is heated 1 hour at 82 DEG C.Coating shows that water-wet behavior, water are easy to soak surface, and finally permeates and apply when lasting exposed Layer.Only show do not have water-wet behavior with the similar coatings of DEMM monomer coats.Which demonstrate polyethylene glycol in the painting based on DEMM The hydrophily assigned in layer.

Embodiment 10

Embodiment 10 be include with methylene malonate monomer block polyalkylene glycol and unreacted methylene The reaction mixture of malonate monomer.The sealing end of polyalkylene glycol is carried out using acid catalyzed ester exchange method.

There is still head, temperature using high vacuum grade lubricating grease and heating mantle (and thermocouple) and magnetic stirring bar assembling Meter, vacuum adapter and three necks (250mL) round-bottomed flask for collecting flask.About 20g is packed into (about in the round-bottomed flask device 0.12mol) DEMM, about 4.6g (about 0.023mol) CARBOWAX^TM200 polyethylene glycol of PEG (can be from DOW CHEMICAL COMPANY is commercially available), about 0.02g (about 1000ppm) MeHQ and about 0.3ml (about 0.0058mol) H₂SO₄Mixture. CARBOWAX^TMThe weight average molecular weight of 200 polyethylene glycol of PEG is about 190 to 210g/ moles, and average hydroxyl value is about 535 to about 590mg KOH/g, fusing point are below about -65 DEG C.The low pressure of about 400mm Hg is kept using vacuum pump during the reaction.Then will Reaction mixture is heated to about 130 DEG C and stir about 2 hours.Ethyl alcohol is collected as byproduct of reaction.Calculate PEG's using NMR Sealing end amount.About 45% DEMM is reacted with PEG, and about 55% DEMM is left monomer.

Embodiment 11

Embodiment 11 is glycerol ethoxylate and unreacted methylene comprising being blocked with methylene malonate monomer The reaction mixture of propylmalonic acid ester monomer.Ester exchange method can be used to carry out for the sealing end of glycerol ethoxylate.

About 30g (about 0.17mol) DEMM, about 3g (about 10 parts/100 parts DEMM) enzyme are packed into 250mL round-bottomed flask 435 antarctic candida isotype B (can be commercially available from NOVOZYME) and about 56g (about 0.056mol) of NOVOZYME is sweet Oily ethoxylate (number-average molecular weight is about 1000, derives from Sigma Aldrich).Flask, which is connected to, has about 200mm Hg The rotary evaporator of low pressure, and 55 DEG C are heated to about for about 8 hours.Ethyl alcohol is removed as byproduct of reaction.Then it uses Tampon in 20ml syringe filters enzyme from product, to separate reaction mixture.The NMR of reaction mixture is obtained as a result, simultaneously It is used for calculating conversion ratio of the glycerol ethoxylate to end-cap product.Observe about 40% required transesterification product (that is, End-cap product).The NMR spectra of reaction mixture is shown in Figure 6.It is believed that reaction mixture includes two substitutions and tri-substituted glycerol Ethoxylate reaction product.Gained reaction mixture include have following structure shown in one or more features sealing end Glycerol ethoxylate.

Reaction mixture is coated in (0.1% benzoic acid in butyl cellosolve caused in advance using Meyer stick 10 Sodium) on cold-rolled steel sheet, after about 24 hours are fully cured at room temperature, about 25 microns of thick coatings are obtained, then at about 82 DEG C Heating about 1 hour.Coating shows that water-wet behavior, water are easy to soak surface, and finally permeation coating when lasting exposed.It compares Under, using only with the reaction mixture preparation of DEMM replacement and solidification (for example, obtaining DEMM homopolymer) under the same conditions The sample of preparation does not show water-wet behavior.Therefore, shown in sealing end glycerol ethoxylate can be used in the coating (for example, In methylene malonate coating, such as based on the coating of DEMM) assign hydrophily.

Embodiment 12

It can be by by the reaction mixture of two pure and mild methylene malonates and one or more other monomers and/or one Kind or the combination of a variety of crosslinking agents are to prepare polymerisable compound.For example, by by the reaction mixture and methylene of embodiment 11 Dimethyl malenate (that is, D3M), DEMM in addition and 1,5 pentanediol DEMM crosslinking agents amount shown in the following table mix to make Standby embodiment 12.

Polymerisable compound is coated in (0.1% benzoic acid in butyl cellosolve caused in advance using Meyer stick 10 Sodium) on cold-rolled steel sheet, after about 24 hours are fully cured at room temperature, obtain 25 microns of thick coatings, then at about 82 DEG C plus Heat about 1 hour.The coating does not show the hydrophilic sexual behaviour seen in embodiment 11 above.This is considered as being crosslinked because of pentanediol It is largely crosslinked and causes provided by agent.By polyol moiety in preparation adjusting final coating (for example, glycerol ethoxylate Object) amount, antifouling properties may be obtained, while keeping durable waterproof coating.

Urethanes/urethane bond

End-caps may include urethanes or urethane bond.It includes isocyanuric acid that this structure, which can be used, It is prepared by the reaction of ester.This structure can be prepared by the method for avoiding the need for any isocyanuric acid ester or isocyanates.For example, ammonia Carbamate key can be by making cyclic carbonate and amine (for example, having one or more, two or more or three or more The compound of multiple amidos) reaction obtained with forming urethane bond and terminal alcohol.Then it can be used terminal alcohol that will contain ammonia The compound of carbamate blocks (for example, via ester exchange reaction) with 1,1- disubstituted olefin compound.Preferably, in amido Each generate carbamate groups, and with 1,1- disubstituted olefin compound sealing end.

Embodiment 13

Embodiment 13 be include with methylene malonate monomer block isocyanuric acid ester ethoxylate and unreacted Methylene malonate monomer reaction mixture.Ester exchange method can be used to carry out for the sealing end of isocyanuric acid ester.

In the 250mL round-bottomed flask with still head, thermometer, vacuum adapter, collection flask and mechanical agitator It is packed into the mixture of about 200g (about 1.16 moles) DEMM and about 0.4g (about 2000ppm) BHT (that is, butylated hydroxytoluene). 1 mole of % sulfuric acid of about 0.6ml is added to round-bottomed flask using syringe when temperature reaches about 40 DEG C by heating mixture In.Next, will 1,3,5- tri- (2- ethoxys) of about 1.0 equivalents (50.6 grams be equal to about 1.94 moles) isocyanuric acid ester is in batches It is added in flask.One of reactant and desired product are shown below:

About 110 DEG C at a temperature of reacted with vigorous stirring under the low pressure of about 500mm Hg about 3 hours.It collects Ethyl alcohol is as byproduct of reaction.As shown in fig. 7, analyzing reaction mixture using H NMR after reaction.Isocyanuric acid ester is to sealing end The conversion ratio of analog is about 30%.

Embodiment 14

By reacting cyclic carbonate with one or more amidos to obtain and there are one or more carbamic acids The compound of ester group and one or more hydroxyls, can prepare in the case where no isocyanates includes urethane bond Compound.Then react hydroxyl to connect 1,1- disubstituted olefin compound.For example, method may include using ring-opening reaction Make cyclic carbonate and diamine reactant to obtain the first step of bisurethane glycol.Preferably cyclic carbonate includes Ethylene carbonate and propylene carbonate.Reaction may include one of feature as shown below or any combination:

The polyalcohol of amido-containing acid ester and 1,1- disubstituted olefin compound react may include in following features one Kind or any combination:

Gained end-caps preferably includes multiple urethane bonds and alkenyl spaced apart.It should be appreciated that alkylene The spacing of group can be controlled by the length of amine-initiated substance.For example, two amidos can be by 4 or more, 6 or more It is a, 10 or more, 15 or more or 20 or more atom separations open.

By the way that ethylene carbonate (for example, about 26.5g, 0.30 mole, 2.0 equivalents) is dissolved in methylene chloride (about Embodiment 14 is prepared in 150ml).Initial heat absorption is observed in course of dissolution, temperature is down to about 0.2 DEG C from about 23 DEG C.So Hexamethylene diamine (about 17.51g, 0.15mol, 1.0 equivalent) is added in solution afterwards.Observe about 10-12 DEG C slight Heat release.Make solution reaction and stir 3 hours, temperature is increased to about 27 DEG C during this period and solution becomes muddy.Then about One hour that the reaction was continued under stiring at 30 DEG C additionally.Reaction product does not dissolve in solvent, and removes from solution.Then it will hang Supernatant liquid is filtered and is washed repeatedly to remove unreacted initial substance.Fig. 8 shows diol intermediates¹³C NMR spectra.

React solid bisurethane glycol filtrate with DEMM.By DEMM (31g, 0.18mol, 5.96 equivalents) and BHT (0.05g) be fitted into equipped with thermocouple and vacuum suction adapter 3 neck round-bottom flasks in. Then solid bisurethane glycol (8.8g, 0.030mol, 1.0 equivalent) is added in flask.Then flask is added Heat is to about 130-135 DEG C.While heating flask, sulfuric acid (0.1mL) is added by syringe.Then decompression (about It is stirred to react under 190mmHg), to effectively remove ethanol byproducts.Greater than about 70 DEG C at a temperature of, suspension is (that is, diamino Ethyl formate glycol) dissolution, obtain the faint yellow clear solution to buff.Then by solution stir about 1 to 1.5 hour, so It cools down under reduced pressure afterwards.Observe simultaneously filtering solid particles.As shown in figure 9, using¹³C NMR monitoring reaction.Fig. 9 A shows pure DEMM 13C NMR spectra.Fig. 9 B shows the mixture of DEMM and urethane esterdiol before adding sulfuric acid.Fig. 9 C, which is shown, to be added Mixture after adding sulfuric acid.Fig. 9 D is shown reacted 1 hour at 135 DEG C after mixture spectrogram.

Claims

1. a kind of functionalization polyol, includes:

Central part, the central part include isocyanurate trimer or have opened by five or more atomic separations Two or more ends；And

Two or more residues of 1,1- disubstituted olefin compound (preferably 1, the olefin(e) compound that 1 dicarbapentaborane replaces), Described in one or two of disubstituted group include ester group；

Wherein the 1,1- bis- replaces each of the residue of 1- olefin(e) compound to be connected to the central part not Same end；So that the functionalized polymeric has at least two olefin functionalities spaced apart.

2. a kind of functionalization polyol, includes:

Centre polymer part, the centre polymer part have two or more ends being spaced apart by multiple monomeric units End, the monomeric unit includes the adjacent monomer unit of covalent bonding；Wherein the centre polymer part is substantially by phase With monomeric unit composition homopolymer, or with including the first monomer and one or more different from first monomer The copolymer of the monomeric unit of comonomer；Wherein the monomeric unit of the centre polymer part is in the site polymerization Each of the end of object part place includes end monomer unit；And

One or more residues of 1,1- disubstituted olefin compound, wherein one or two of described disubstituted group includes Ester group；

Wherein the 1,1- bis- replaces each of the residue of 1- olefin(e) compound to be connected to the centre polymer portion The different ends (that is, the different end monomer units for being connected to the centre polymer part) divided；So that the functionalized poly Closing object has at least one olefin functionalities；

Wherein the functionalization polyol is functionalized polymeric.

3. a kind of functionalization polyol, includes:

Polymerized polyalcohol with two or more ends, wherein the one or more in the end replaces alkene with 1,1- bis- The residue of hydrocarbon compound blocks, wherein the functionalization polyol is functionalized polymeric.

4. functionalization polyol according to any one of claim 1 to 3, wherein 1, the 1- disubstituted olefin The number of the residue of compound is two or more, and the functionalization polyol includes by the center Polymer moieties multiple alkenyls spaced apart.

5. functionalization polyol according to any one of claim 1 to 4, wherein the central part is center Polymer moieties and the residue including having the polyalcohol of two or more primary oh groups, wherein 1, the 1- bis- replaces 1- Each of described residue of olefin(e) compound is connected to the residue of the polyalcohol by ester bond.

6. functionalization polyol according to any one of claim 1 to 5, wherein the central part is center Polymer moieties and including ehter bond or ester bond.

7. functionalization polyol according to any one of claim 1 to 6, wherein the central part is isocyanide Urea acid esters tripolymer.

8. functionalization polyol according to any one of claim 1 to 7, wherein the central part is to include Polyester, polyethers, polybutadiene, polycarbonate, polymer containing acrylic acid, the polymer of silicone-containing or any combination of them Centre polymer part.

9. functionalization polyol according to any one of claim 1 to 8, wherein about the 50 of the central part Weight % or more is the polymer of polyester, polyethers, polybutadiene, polycarbonate, polymer containing acrylic acid or silicone-containing.

10. functionalization polyol according to claim 9, wherein the Weight-average molecular of the centre polymer part Amount is about 300 or bigger.

11. functionalization polyol according to any one of claim 1 to 4, wherein the central part is single Body compound.

12. functionalization polyol according to any one of claim 1 to 11, wherein 1, the 1- bis- replaces alkene Hydrocarbon be have double bond be bonded to another carbon atom central carbon atom 1,1- disubstituted ethylene, wherein the central carbon atom Further it is bonded to two carbonyls.

13. functionalization polyol according to any one of claim 1 to 12, wherein 1, the 1- bis- replaces alkene Hydrocarbon includes one or more other central carbon atom, and respectively double bond is bonded to another carbon atom and goes forward side by side the central carbon atom One step is bonded to two carbonyls (for example, dimer or tripolymer or longer oligomer).

14. functionalization polyol according to any one of claim 1 to 12, wherein 1, the 1- bis- replaces alkene Hydrocarbon compound is methylene malonate.

15. according to claim 1 to functionalization polyol described in any one of 14, wherein the central part includes Siloxanes, polybutadiene, isocyanuric acid ester or the polyethylene glycol that aliphatic polyester, aromatic polyester, polyethers, methanol block.

16. according to claim 1 to functionalization polyol described in any one of 15 (for example, the functionalization polymerize Object), wherein the residue of 1, the 1- disubstituted olefin monomer is that 1, the 1- bis- having following structure replaces the residue of ester:

Wherein R¹May respectively be at each occurrence can be containing one or more heteroatomic alkyl.

17. according to claim 1 to functionalization polyol described in any one of 15, wherein the central part is virtue The residue of adoption ester polyol or the residue of aliphatic polyester polylol.

18. according to claim 1 to functionalization polyol described in any one of 17, wherein the central part is poly- The residue of carbonate polyol or the residue of polybutadiene polyol.

19. functionalization polyol according to claim 17, wherein the centre polymer part includes following In butadiene repeat units

1-2 configuration (that is,)

1-4 cis-configuration,

1-4 anti-configuration,

Or any combination of them；

Wherein the number of butadiene repeat units is about 3 or more (preferably about 5 in the centre polymer part Or more).

20. according to claim 1 to functionalization polyol described in any one of 15, wherein the central part is to make For methanol sealing end siloxanes residue centre polymer part, wherein the siloxane unit along the centre polymer part Number be about 3 or more.

21. according to claim 1 to functionalization polyol described in any one of 15, wherein during the central part is Heart polymer moieties, and being includes one or more ethylene glycol repeat units, one or more propylene glycol repetitive units, one Or the residue of the polyalkylene glycol of multiple butanediol repetitive units or any combination of them, wherein aklylene glycol repeats single The number of member is about 3 or more.

22. according to claim 1 to functionalization polyol described in any one of 22, wherein the functionalization polyhydroxy Compound includes by described 1,1, and disubstituted olefin compound is connected to the urethane bond of the central part.

23. a kind of ester exchange method, comprising the following steps:

At least intermediate polymer and 1,1- disubstituted olefin compound of the mixing with terminal OH groups；And

React the intermediate polymer and 1, the 1- disubstituted olefin compound, wherein in the disubstituted group extremely Few one is ester, so that 1, the 1- disubstituted olefin compound is located at the end of the polymer.

24. a kind of method includes the steps that being crosslinked functionalization polyol described in any one of claim 1 to 23.

25. a kind of polymer, the polymer includes one or more 1,1- disubstituted olefin compounds and right by polymerization It is required that the composition of functionalization polyol described in any one of 3 to 23 (for example, described functionalized polymeric) and make Standby, (for example, coming from described functionalized polymeric) includes the enough polyalcohol and enough described wherein the composition 1,1- disubstituted olefin compound (for example, malonate, such as methylene malonate), so that the polymer is (for example, handing over When connection/polymerization 1,1- disubstituted olefin compound) show the glass of two kinds of differences (preferably differing about 20 DEG C or more) Change the melting temperature of transition temperature and/or two kinds of differences (preferably differing about 20 DEG C or more) (for example, related to the polyalcohol A glass transition temperature and/or melting temperature and a glass transition temperature relevant to polymethylene malonate Degree and/or melting temperature).

26. according to claim 1 to functionalization polyol described in any one of 23 (for example, the functionalization polymerize Object), wherein the functionalization polyol include urethane bond (for example, for by described 1,1, disubstituted olefin Compound is connected to the central part).

27. a kind of method for forming functionalization polyol described in any one of claim 1 to 23, including following step It is rapid:

Bis- substituted compound of 1,1- is continuously fed into reactor；

Polymerized polyalcohol (for example, polybutadiene polymers of polyhydroxy sealing end) is continuously fed into the reactor；

The continuous flowing reactive for carrying out 1,1-, bis- substituted compound and the polymerized polyalcohol in the presence of a catalyst, makes It obtains and forms the functionalization polyol via ester exchange reaction.